Process for producing cyclic olefin based polymers, cyclic olefin copolymers, compositions and molded articles comprising the copolymers

ABSTRACT

A process for effectively producing a cyclic olefin polymer and a cyclic olefin/alpha-olefin copolymer without opening the cyclic olefin, is disclosed. Further, a novel cyclic olefin/alpha-olefin copolymer prepared by the above-mentioned process, compositions and molded articles comprising the novel copolymer, are also disclosed. In the process for producing a cylcic olefin based polymer according to the present invention, homopolymerization of a cyclic olefin or copolymerization of a cyclic olefin and an alpha-olefin is effected in the presence of a catalyst comprising, as main ingredients, the following Compounds (A) and (B), and optionally Compound (C): 
     (A) a transition metal compound; 
     (B) a compound capable of forming an ionic complex when reacted with a transition metal compound; and 
     (C) an organoaluminum compound.

FIELD OF THE INVENTION

The present invention relates to a process for producing a cyclic olefinbased polymer, and particularly relates to a process for producing acyclic olefin polymer and a cyclic olefin/alpha-olefin copolymer withoutopening rings of the cyclic olefin.

Further, the present invention relates to a novel cyclicolefin/alpha-olefin copolymer, and a composition and a molded articlecomprising the copolymer.

RELATED ART

It is known that cyclic olefins can be polymerized in the presence of aZiegler-Natta catalyst. In most of the cases, the cyclic olefins sufferring opening during the polymerization to give polymers with openedrings.

On the contrary to this process, cyclic olefins can be polymerizedwithout suffering ring opening in accordance with the following methods(a) to (e).

(a) Japanese Patent Application Laid-Open Gazette (Kokai) No. Sho64-66216 describes a process for polymerizing a cyclic olefin withoutsuffering ring opening to obtain an isotactic polymer, in the presenceof a catalyst composed of a stereo-rigid metallocene compound,particularly ethylenebis(indenyl)zirconium dichloride, and aluminoxane.

(b) Kokai No. Sho 61-271308 discloses a process for copolymerizing acyclic olefin and an alpha-olefin without suffering ring opening, in thepresence of a catalyst composed of a soluble vanadium compound and anorganoaluminum compound.

(c) Kokai No. Sho 61-221206 and Kokai No. 64-106 describe a process forcopolymerizing a cyclic olefin and an alpha-olefin without sufferingring opening, in the presence of a catalyst composed of a transitionmetal compound and aluminoxane.

(d) Kokai No. Sho 62-252406 describes a process for producing anethylene/cyclic,olefin random copolymer having an ethylene content of 40to 90 mol % with the use of a catalyst composed of a soluble vanadiumcompound and an organoaluminum compound.

(e) Kokai No. Hei 3-45612 discloses a process for producing ahomopolymer and a copolymer of a polycyclic olefin with the use of acatalyst composed of a specific metallocene compound and aluminoxane.

However, the polymerization processes (a), (c) and (d) require use of agreat amount of aluminoxane. Thus, a substantial amount of a metal willremain in the polymerized products, resulting in deterioration andcoloring of the products. In these processes, after polymerization,deashing treatment of the resultant products should be sufficientlyconducted. Thus, these processes have a problem in productivity.

Further, the catalysts used in the processes (b) and (d) are inferiordue to extremely poor catalytic activities. In addition, anethylene-rich copolymer obtained by the process (d) shows clear meltingpoint and poor random configuration. Furthermore, in Kokai No. Sho3-45612 (Process (e)), it is not proved in the working examples that acopolymer having a cyclic olefin content of 40 mol % or more can beproduced.

On the other hand, studies on olefin polymerization with use of acationic transition metal complex, have been made since many years ago.There are many reports as indicated as follows. However, each processhas some problems.

(f) Natta et al. reported that ethylene can be polymerized in thepresence of a catalyst composed of titanocene dichloride andtriethylaluminum (J. Polymer Sci., 26, 120 (1964). Further, Breslow etal. reported polymerization of ethylene with use of a titanocenedichloride/dimethylaluminum chloride catalyst (J. Am. Chem. Soc., 79,5072 (1957). Furthermore, Dyachkovskii et al. suggested thatpolymerization activities in ethylene polymerization using a titanocenedichloride/dimethylaluminum chloride catalyst are derived from atitanocenemonomethyl cation (J. Polymer Sci., 16, 2333 (1967).

However, the ethylene activities in these processes are extremely low.

(g) Jordan et al. reported synthesis and isolation of[biscyclopentadienylzirconium methyl(tetrahydrofuran)][tetraphenylboricacid] resulting from the reaction of zirconocenedimethyl and silvertetraphenylborate, and ethylene polymerization using the thussynthesized compound (J. Am. Chem. Soc., 108, 7410 (1986). Further,Jordan et al. synthesized and isolated [biscyclopentadienylzirconiumbenzyl(tetrahydrofuran)][tetraphenylboric acid] resulting from thereaction of zirconocenedibenzyl and ferrocenium tetraphenylborate (J.Am. Chem. Soc., 109, 4111 (1987).

It was confirmed that ethylene can be slightly polymerized using thesecatalysts, however, their polymerization activities are extremely low.

(h) Turner et al. have proposed a process for polymerizing analpha-olefin in the presence of a catalyst comprising a metallocenecompound and a boric acid complex containing a specific amine such astriethylammonium tetraphenylborate, triethylammonium tetratolylborate,and triethylammonium tetra(pentafluorophenyl)borate (Japanese PatentApplication PCT Laid-Open Gazette No. Sho 1-502036).

However, in this gazette, there is no description about copolymerizationof an alpha-olefin and a cyclic olefin. Further, the catalysts haveextremely low polymerization activities and thus this process is notsuitable for industrial use.

In addition, polymerization of acyclic olefin is not reported in any oneof the technical literature or the patent gazettes (F) to (h).

DISCLOSURE OF THE INVENTION

The present invention was made in view of the above-mentionedsituations, and provides a process for producing a cyclic olefin basedpolymer as described below.

Production Process of Cyclic Olefin Based Polymers:

The present invention provides a process for producing a cyclic olefinbased polymer wherein homopolymerization of a cyclic olefin orcopolymerization of a cyclic olefin and an alpha-olefin is carried outin the presence of a catalyst comprising, as main components, thefollowing compounds (A) and (B) and optionally the following compound(C):

(A) a transition metal compound;

(B) a compound capable of forming an ionic complex when reacted with atransition metal compound; and

(C) an organoaluminum compound.

The above-mentioned catalysts show excellent polymerization activitiesfor the homopolymerization of a cyclic olefin or the copolymerization ofa cyclic olefin and an alpha-olefin. In particular, the catalystcomprising the organoaluminum compound (C) shows extremely highpolymerization activities with use of a small amount of anorganoaluminum compound. Therefore, according to the above productionprocess, a cyclic olefin homopolymer or an cyclic olefin/alpha-olefincopolymer can be effectively produced without ring-opening during thepolymerization and without use of a great amount of an organoaluminumcompound.

Further, the present invention provides the following novel cyclicolefin copolymers (I) and (II) which can be produced by, for example,the above-mentioned process.

Cyclic Olefin Copolymers (I).

The cyclic olefin copolymers (I) have a repeating unit represented bythe following general formula [X]: ##STR1## (wherein R^(a) is a hydrogenatom or a hydrocarbon group having 1 to 20 carbon atoms); and arepeating unit represented by the following formula [Y]: ##STR2##(wherein R^(b) to R^(m) are independently a hydrogen atom, a hydrocarbongroup having 1 to 20 carbon atoms or a substituent having a halogenatom, oxygen atom or nitrogen atom; n is an integer of at least 0; R^(j)or R^(k) and R^(l) or R^(m) may form a ring together; and R^(b) to R^(m)may be the same as or different from each other).

The cyclic olefin copolymers (I) have (1) 0.1 to 40 mol % of therepeating unit of the formula [X] and 60 to 99.9 mol % of the repeatingunit of the formula [Y]; (2) an intrinsic viscosity [η] of 0.01 to 20dl/g; and (3) a glass transition temperature (Tg) of 150°to 370° C.

The above cyclic olefin copolymers (I) have high content of therepeating unit based on a cyclic olefin and mainly have a vinylenestructure. Thus, the copolymers are novel ones obtained for the firsttime by the process according to the present invention. The cyclicolefin copolymers (I) are superior in heat resistance, transparency,strength and rigidness, and can be effectively used in optical, medicaland food fields.

Cyclic Olefin Copolymers (II):

Cyclic olefin copolymers (II) are those having (1) 80 to 99.9 mol % ofthe repeating unit of Formula [X] and 0.1 to 20 mol % of the repeatingunit of Formula [Y]; (2) an intrinsic viscosity [η] of 0.01 to 20 dl/g;(3) a glass transition temperature (Tg) of less than 30° C.; and (4) atensile modulus of less than 2,000 Kg/cm².

The above cyclic olefin copolymers (II) have low content of therepeating unit based on a cyclic olefin, and are flexible resins havingphysical properties different from those of polymers obtained by knowncatalyst systems. Thus, the copolymers are novel ones obtained for thefirst time by the process according to the present invention. The cyclicolefin copolymers (II) have an excellent elongation recovery property,good transparency, suitable elasity and well-balanced physicalproperties, and can be effectively used as films, sheets and materialsfor various molded articles in a variety of application fields such aswrapping, medical and agricultural fields.

Further, the present invention provides the following compositionscomprising the above novel cyclic olefin copolymers (II).

Cyclic Olefin Copolymer Compositions:

The present invention provides a cyclic olefin copolymer composition(First Composition) comprising the following components (a) and (b), anda cyclic olefin copolymer composition (Second Composition) comprisingthe following components (a), (b) and (c).

(a) 100 parts by weight of the cyclic olefin copolymer (II);

(b) 0.01 to 10 parts by weight of an anti-blocking agent and/orlubricant; and

(c) 1 to 100 parts by weight of an alpha-olefin based copolymer.

The above first and second compositions exhibit good moldability ininflation molding and the like as well as a good elongation recoveryproperty, good transparency and suitable elasity. Thus, the compositionscan be suitably used as materials for films and sheets in wrapping,medical and agricultural fields.

Further, the present invention provides the following molded articlesprepared from the above-mentioned cyclic olefin copolymers or theabove-mentioned cyclic olefin copolymer compositions.

Molded Article:

The molded articles include, for example, films, sheets, wrapping filmsand those made by using a mold as indicated in the following examples(1) to (5):

(1) Films or sheets made of the cyclic olefin copolymer (I);

(2) Films or sheets made of the cyclic olefin copolymer (II);

(3) Wrapping films made of the cyclic olefin copolymer (II)

(4) Articles made using a mold from the cyclic olefin copolymer (II);and

(5) Films or sheets made of the cyclic olefin copolymer composition (thefirst composition or the second composition).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the flowchart of the production process of the presentinvention;

FIG. 2 shows the DSC chart of the copolymer obtained in Example 88;

FIG. 3 shows the DSC chart of the copolymer obtained in ComparativeExample 11;

FIG. 4 is the ¹³ C-NMR chart of the copolymer obtained in Example 91;

FIG. 5 is the DSC chart (heat down stage) of the copolymer obtained inExample 118; and

FIG. 6 is the DSC chart (heat down stage) of the copolymer obtained inComparative Example 18.

BEST EMBODIMENTS OF THE INVENTION

The present invention will be described in more detail below.

Production Process of Cyclic Olefin Based Polymers:

FIG. 1 shows the production process according to the present invention.

In the process of the production of the cyclic olefin based polymersaccording to the present invention, transition metal compound may beused as Compound (A). The transition metal compounds include, forexample, those containing at least one transition metal belonging to theIVB, VB, VIB, VIIB and VIII Groups of the Periodic Table. Morespecifically, as the above transition metals, preferred are titanium,zirconium, hafnium, chromium, manganese, nickel, palladium and platinum.Of these, more preferred are zirconium, hafnium, titanium, nickel andpalladium.

Suitable transition metal compounds include a variety of compounds,particularly include those containing at least one transition metalbelonging to the IVB and VIII Groups of the Periodic Table, moresuitably a metal of the IVB Group, i.e., titanium (Ti), zirconium (Zr)or hafnium (Hf). More preferred are cyclopentadienyl compoundsrepresented by the following formula (I), (II) or (III), or derivativesthereof, or compounds represented by the following formula (IV) orderivatives thereof.

    CpM.sup.1 R.sup.1 aR.sup.2 bR.sup.3 c                      (I)

    Cp.sub.2 M.sup.1 R.sup.1 dR.sup.2 e                        (II)

    (Cp-Af-Cp)M.sup.1 R.sup.1 dR.sup.2 e                       (III)

    M.sup.1 R.sup.1 gR.sup.2 hR.sup.3 iR.sup.4 j               (IV)

In Formulas (I) to (IV), M¹ is a Ti, Zr or Hf atom; Cp is an unsaturatedcyclic hydrocarbon group or chain cyclic hydrocarbon group such as acyclopentadienyl group, substituted cyclopentadienyl group, indenylgroup, substituted indenyl group, tetrahydroindenyl group, substitutedtetrahydroindenyl group, fluorenyl group or substituted fluorenyl group;R¹, R², R³ and R⁴ are independently a hydrogen atom, oxygen atom,halogen atom, C₁₋₂₀ alkyl group, C₁₋₂₀ alkoxy group, aryl group,alkylaryl group, C₆₋₂₀ arylalkyl group, C₁₋₂₀ acyloxy group, allylgroup, substituted allyl group, a ligand having a sigma bond such as asubstituent containing a silicon atom, chelate ligand or Lewis baseligand such as an acetylacetonate group and substituted acetylacetonategroup; A is a bridge based on a covalent bond; a, b and c areindependently an integer of 0 to 3; d and e are independently an integerof 0 to 2; f is an integer of 0 to 6; g, h, i and j are independently aninteger of 0to 4; two or more of R¹ and R², R³ and R⁴ may form a ring.If the above-mentioned Cp has a substituent, the substituent ispreferably a C₁₋₂₀ alkyl group. In Formulas (II) and (III), two of Cpmay be the same as or different from each other.

In the above Formulas (I) to (III), the substituted cyclopentadienylgroups include, for example, a methylcyclopentadienyl group,ethylcyclopentadienyl group, isopropylcyclopentadienyl group,1,2-dimethylcyclopentadienyl group, tetramethylcyclopentadienyl group,1,3-dimethylcyclopentadienyl group, 1,2,3-trimethylcyclopentadienylgroup, 1,2,4-trimethylcyclopentadienyl group,pentamethylcyclopentadienyl group, and trimethylsilylcyclopentadienylgroup.

Examples of R¹ to R⁴ include halogen atoms such as a fluorine atom,chlorine atom, bromine atom and iodine atom; C₁₋₂₀ alkyl groups such asa methyl group, ethyl group, n-propyl group, isopropyl group, n-butylgroup, octyl group and 2-ethylhexyl group; C₁₋₂₀ alkoxy groups such as amethoxy group, ethoxy group, propoxy group, butoxy group and phenoxygroup; C₆₋₂₀ aryl groups alkylaryl groups or arylalkyl group, such as aphenyl group, tolyl group, xylyl group and benzyl group; C₁₋₂₀ acyloxygroups such as a heptadecylcarbonyloxy group; substituents containing asilicon atom such as a trimethylsilyl group, (trimethylsilyl)methylgroup; Lewis bases such as ethers including dimethyl ether, diethylether and tetrahydrofuran, thioethers including tetrahydrothiophene,esters including ethylbenzoate, nitriles including acetonitrile andbenzonitrile, amines including trimethylamine, triethylamine,tributylamine, N, N-dimethylaniline, pyridine, 2,2'-bipyridine andphenanthroline, and phosphines including triethylphosphine andtriphenylphosphine; chain unsaturated hydrocarbons such as ethylene,butadiene, 1-pentene, isoprene, pentadiene, 1-hexene and derivativesthereof; unsaturated cyclic hydrocarbons such as benzene, toluene,xylene, cycloheptatriene, cyclooctadiene, cyclooctatriene,cyclooctatetraene and derivatives thereof. The bridges based on acovalent bond, A include, for example, a methylene bridge,dimethylmethylene bridge, ethylene bridge, 1,1'-cyclohexylene bridge,dimethylsilylene bridge, dimethylgermanylene bridge anddimethylstannylene bridge.

More specifically, these compounds include the following compounds, andthose having titanium or hafnium instead of zirconium.

Compounds of Formula (I):

(Pentamethylcyclopentadienyl)trimethylzirconium,

(pentamethylcyclopentadienyl)triphenylzirconium,

(pentamethylcyclopentadienyl)tribenzylzirconium,

(pentamethylcyclopentadienyl)trichlorozirconium,

(pentamethylcyclopentadienyl)trimethoxyzirconium,

(cyclopentadienyl)trimethylzirconium,

(cyclopentadienyl)triphenylzirconium,

(cyclopentadienyl)tribenzylzirconium,

(cyclopentadienyl)trichlorozirconium,

(cyclopentadienyl)trimethoxyzirconium,

(cyclopentadienyl)dimethyl(methoxy)zirconium,

(methylcyclopentadienyl)trimethylzirconium,

(methylcyclopentadienyl)triphenylzirconium,

(methylcyclopentadienyl)tribenzylzirconium,

(methylcyclopentadienyl)trichlorozirconium,

(methylcyclopentadienyl)dimethyl(methoxy)zirconium,

(dimethylcyclopentadienyl)trichlorozirconium,

(trimethylcyclopentadienyl)trichlorozirconium,

(trimethylsilylcyclopentadienyl)trimethylzirconium,

(tetramethylcyclopentadienyl)trichlorozirconium,

Compounds of Formula (II):

Bis(cyclopentadienyl)dimethylzirconium,

bis(cyclopentadienyl)diphenylzirconium,

bis(cyclopentadienyl)diethylzirconium,

bis(cyclopentadienyl)dibenzylzirconium,

bis(cyclopentadienyl)dimethoxyzirconium,

bis(cyclopentadienyl)dichlorolzirconium,

bis(cyclopentadienyl)dihydridezirconium,

bis(cyclopentadienyl)monochloromonohydridezirconium,

bis(methylcyclopentadienyl)dimethylzirconium,

bis(methylcyclopentadienyl)dichlorozirconium,

bis(methylcyclopentadienyl)dibenzylzirconium,

bis(pentamethylcyclopentadienyl)dimethylzirconium,

bis(pentamethylcyclopentadienyl)dichlorozirconium,

bis(pentamethylcyclopentadienyl)dibenzylzirconium,

bis(pentamethylcyclopentadienyl)chloromethylzirconium,

bis(pentamethylcyclopentadienyl)hydridemethylzirconium,

(cyclopentadienyl)(pentamethylcyclopentadienyl)dichlorozirconium.

Compounds of Formula (III):

Ethylenebis(indenyl)dimethylzirconium,

ethylenebis(indenyl)dichlorozirconium,

ethylenebis(tetrahydroindenyl)dimethylzirconium,

ethylenebis(tetrahydroindenyl)dichlorozirconium,

dimethylsilylenebis(cyclopentadienyl)dimethylzirconium,

dimethylsilylenebis(cyclopentadienyl)dichlorozirconium,

isopropyl(cyclopentadienyl)(9-fluorenyl)dimethylzirconium,

isopropyl(cyclopentadienyl)(9-fluorenyl)dichlorozirconium,

[phenyl(methyl)methylene](9-fluorenyl)(cyclopentadienyl)dimethylzirconium,

diphenylmethylene(cyclopentadienyl)(9-fluorenyl)dimethylzirconium,

ethylidene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium,

cyclohexyl(9-fluorenyl)(cyclopentadienyl)dimethylzirconium,

cyclopentyl(9-fluorenyl)(cyclopentadienyl)dimethylzirconium,

cyclobutyl(9-fluorenyl)(cyclopentadienyl)dimethylzirconium,

dimethylsilylene(9-fluorenyl)(cyclopentadienyl)dimethylzirconium,

dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)dichlorozirconium,

dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)dimethylzirconium,

dimethylsilylenebis(indenyl)dichlorozirconium.

Further, compounds other than the cyclopentadienyl compound representedby Formula (I), (II) or (III) do not adversely affect themeritorious-effects of the present invention. Examples of such compoundsinclude those compounds represented by Formula (IV), such astetramethylzirconium, tetrabenzylzirconium, tetramethoxyzirconium,tetraethoxyzirconium, tetrabutoxyzirconium, tetrachlorozirconium,tetrabromozirconium, butoxytrichlorozirconium,dibutoxydichlorozirconium, bis(2,5-di-t-butylphenoxy)dimethylzirconium,bis(2,5-di-t-butylphenoxy)dichlorozirconium, and zirconiumbis(acetylacetonate). The other examples include compounds basicallysame as the above compounds except that zirconium is replaced withhafnium or titanium. Such compounds include zirconium compounds, hafniumcompounds and titanium compounds having at least one group selected fromalkyl groups, alkoxy groups and halogen atoms.

Further, the transition metal compounds containing a transition metalbelonging to the VIII Group, are not particularly limited. Examples ofchromium compounds include tetramethylchromium, tetra(t-butoxy)chromium,bis(cyclopentadienyl)chromium,hydridetricarbonyl(cyclopentadienyl)chromium,hexacarbonyl(cyclopentadienyl)chromium, bis(benzene)chromium,tricarbonyltris(phosphonic acid triphenyl)chromium, tris(aryl)chromium,triphenyltris(tetrahydrafuran)chromium and chromiumtris(acetylacetonate).

Examples of manganese compounds includetricarbonyl(cyclopentadienyl)manganese, pentacarbonylmethylmanganese,bis(cyclopentadienyl)manganese and manganese bis(acetylacetonate).

Examples of nickel compounds includedicarbonylbis(triphenylphosphine)nickel,dibromobis(triphenylphosphine)nickel, dinitrogenbis(bis(tricyclohexylphosphine)nickel),chlorohydridebis(tricyclohexylphosphine)nickel,chloro(phenyl)bis(triphenylphosphine)nickel,dimethylbis(trimethylphosphine)nickel, diethyl(2,2'-bipyridyl)nickel,bis(allyl)nickel, bis(cyclopentadienyl)nickel,bis(methylcyclopentadienyl)nickel,bis(pentamethylcyclopentadienyl)nickel, allyl(cyclopentadienyl)nickel,(cyclopentadienyl)(cyclooctadiene)nickel tetrafluoroborate,bis(cyclooctadiene)nickel, nickel bisacetylacetonate, allylnickelchloride, tetrakis(triphenylphosphine)nickel, nickel chloride, (C₆H₅)Ni[OC(C₆ H₅)CH═P(C₆ H₅)₂ ][P(C₆ H₅)₃ ], and (C₆ H₅)Ni[OC(C₆ H₅)C(SO₃Na)═P(C₆ H₅)₂ [P(C₆ H₅)₃ ].

Examples of palladium compounds includedichlorobis(benzonitrile)palladium,carbonyltris(triphenylphosphine)palladium,dichlorobis(triethylphosphine)palladium, bis(isocyanatedt-butyl)palladium, palladium bis(acetylacetonate),dichloro(tetraphenylcyclobutadiene)palladium,dichloro(1,5-cyclooctadiene)palladium, allyl(cyclopentadienyl)palladium,bis(allyl)palladium, allyl(1,5-cyclooctadiene)palladium, palladiumtetrafluoroborate, (acetylacetonate)(1,5-cyclooctadiene)palladiumtetrafluoroborate and tetrakis(acetonitrile)palladiumbistetrafluoroborate.

Further, Compounds (B) are not particularly limited to, but include anycompounds capable of forming an ionic Complex when reacted with thetransition metal compound (A). The suitable compounds as Compounds (B)include a compound comprising a cation and an anion wherein a pluralityof functional groups are connected to an element, particularly acoordination complex compound. The compounds comprising a cation and ananion wherein a plurality of functional groups are connected to anelement, include, for example, those compounds represented by thefollowing formula (V) or (VI):

    ([L.sup.1 -R.sup.7 ].sup.k+).sub.p ([M.sup.3 Z.sup.1 Z.sup.2 . . . Z.sup.n ].sup.(n-m)-).sub.q                                       (V)

    ([L.sup.2 ].sup.k+).sub.p ([M.sup.4 Z.sup.1 Z.sup.2 . . . Z.sup.n ].sup.(n-m)-).sub.q                                       (VI)

wherein L² is M⁵, R⁸ R⁹ M⁶, R¹⁰ ₃ C or R¹¹ M⁶.

In Formula (V) or (VI), L¹ is a Lewis base; M³ and M⁴ are independentlyan element selected from the groups of VB, VIB, VIIB, VIII, IB, IIB,IIIA, IVA and VA of the Periodic Table; M⁵ and M⁶ are independently anelement selected from the groups of IIIB, IVB, VB, VIB, VIIB, VIII, IA,IB, IIA, IIB and VIIA of the Periodic Table; Z¹ to Z^(n) areindependently a hydrogen atom, dialkylamino group, C₁₋₂₀ alkoxy group,C₆₋₂₀ aryloxy group, C₁₋₂₀ alkyl group, C₆₋₂₀ aryl group, alkylarylgroup, arylalkyl group, C₁₋₂₀ halogenated hydrocarbon group, C₁₋₂₀acyloxy group, organometalloid group or halogen atom; two or more of Z¹to Z^(n) may form a ring; R⁷ is a hydrogen atom, C₁₋₂₀ alkyl group,C₆₋₂₀ aryl group, alkylaryl group or aryl alkyl group; R⁸ and R⁹ areindependently a cyclopentadienyl group, substituted cyclopentadienylgroup, indenyl group or fluorenyl group; R¹⁰ is a C₁₋₂₀ alkyl group,aryl group, alkylaryl group or arylalkyl group; R¹¹ is a large ringligand such as tetraphenylporphyrin and phthalocyanine; m is a valencyof M³ and M⁴ and is an integer of 1 to 7; n is an integer of 2 to 8; kis an ion value number of [L¹ -R⁷ ] and [L² ], and is an integer of 1 to7; and p is an integer of at least 1; and q is specified by the formula:q=(p×k)/(n-m).

Examples of the above Lewis bases are amines such as ammonium,methylamine, aniline, dimethylamine, diethylamine, N-methylaniline,diphenylamine, trimethylamine, triethylamine, tri-n-butylamine,N,N-dimethylaniline, methyldiphenylamine, pyridine,p-bromo-N,N-dimethylaniline and p-nitro-N,N-dimethylaniline; phosphinessuch as triethylphosphine, triphenylphosphine and diphenylphosphine;ethers such as dimethyl ether, diethyl ether, tetrahydrofuran anddioxane; thioethers such as diethyl thioethers and tetrahydrothiophene;and esters such as ethylbenzoate.

Examples of M³ and M⁴ are, for example, B, Al, Si, P, As and Sb.Examples of M⁵ are Li, Na, Ag, Cu, Br, I and I₃. Examples of M⁶ are Mn,Fe, Co, Ni and Zn. Examples of Z¹ to Z^(n) include dialkylamino groupssuch as a dimethylamino group and diethylamino group; C₁₋₂₀ alkoxygroups such as a methoxy group, ethoxy group and n-butoxy group; C₆₋₂₀aryloxy groups such as phenoxy group, 2,6-dimethylphenoxy group andnaphthyloxy group; C₁₋₂₀ alkyl groups such as a methyl group, ethylgroup, n-propyl group, iso-propyl group, n-butyl group, n-octyl groupand 2-ethylhexyl group; C₆₋₂₀ aryl, alkylaryl or arylalkyl groups suchas a phenyl group, p-tolyl group, benzyl group, 4-t.-butylphenyl group,2,6-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4-dimethylphenylgroup, 2,3-dimethylphenyl group; C₁₋₂₀ halogenated hydrocarbon groupssuch as p-fluorophenyl group, 3,5-difluorophenyl group,pentachlorophenyl group, 3,4,5-trifluorophenyl group, pentafluorophenylgroup, 3,5-di(trifluoromethyl)phenyl group; halogen atoms such as F, Cl,Br and I; organometalloid groups such as a pentamethylantimony group;trimethylsilyl group, trimethylgermanyl group, diphenylarsine group,dicyclohexylantimony group and diphenylboron group. Examples of R⁷ andR¹⁰ are the same as above. Examples of substituted cyclopentadienylgroups represented by R⁸ and R⁹ include those substituted with an alkylgroup such as a methylcyclopentadienyl group, butylcyclopentadienylgroup and pentamethylcyclopentadienyl group. Usually, the alkyl groupshave 1 to 6 carbon atoms and the number of substituted alkyl groups isan integer of 1 to 5. In Formula (V) or (VI), M³ and M⁴ are preferablyboron.

Of those compounds represented by Formula (V) or (VI), the followingcompounds can be particularly used as preferred ones.

Compounds Represented by Formula

Triethylammonium tetraphenylborate, tri(n-butyl)ammoniumtetraphenylborate, trimethylammonium tetraphenylborate,

tetraethylammonium tetraphenylborate, methyltri(n-butyl)ammoniumtetraphenylborate, benzyltri(n-butyl)ammonium tetraphenylborate,

dimethyldiphenylammonium tetraphenylborate,

methyltriphenylammonium tetraphenylborate,

trimethylanilinium tetraphenylborate,

methylpyridinium tetraphenylborate,

benzylpyridinium tetraphenylborate,

methyl(2-cyanopyridinium) tetraphenylborate,

trimethylsulfonium tetraphenylborate,

benzyldimethylsulfonium tetraphenylborate,

triethylammonium tetrakis(pentafluorophenyl)borate,

tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

triphenylammonium tetrakis(pentafluorophenyl)borate,

tetrabutylammonium tetrakis(pentafluorophenyl)borate,

tetraethylammonium tetrakis(pentafluorophenyl)borate,

methyltri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

benzyltri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

methyldiphenylammonium tetrakis(pentafluorophenyl)borate,

methyltriphenylammonium tetrakis(pentafluorophenyl)borate,

dimethyldiphenylammonium tetrakis(pentafluorophenyl)borate,

anilinium tetrakis(pentafluorophenyl)borate, methylaniliniumtetrakis(pentafluorophenyl)borate,

dimethylanilinium tetrakis(pentafluorophenyl)borate,

trimethylanilinium tetrakis(pentafluorophenyl)borate,

dimethyl(m-nitroanilinium) tetrakis(pentafluorophenyl)borate,

dimethyl(p-bromoanilinium) tetrakis(pentafluorophenyl)borate,

pyridinium tetrakis(pentafluorophenyl)borate, p-cyanopyridiniumtetrakis(pentafluorophenyl)borate,

N-methylpyridinium tetrakis(pentafluorophenyl)borate,

N-benzylpyridinium tetrakis(pentafluorophenyl)borate,

O-cyano-N-methylpyridinium tetrakis(pentafluorophenyl)borate,

p-cyano-N-methylpyridinium tetrakis(pentafluorophenyl)borate,

p-cyano-N-benzylpyridinium tetrakis(pentafluorophenyl)borate,

trimethylsulfonium tetrakis(pentafluorophenyl)borate,

benzyldimethylsulfonium tetrakis(pentafluorophenyl)borate,

tetraphenylphosphonium tetrakis(pentafluorophenyl)borate,

dimethylanilinium tetrakis(3,5-ditrifluoromethylphenyl)borate, andhexafluoroarsenic acid triethylammonium.

Compounds Represented by Formula (VI):

Ferrocenium tetraphenylborate, silver tetraphenyl borate, trityltetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate,ferrocenium tetrakis(pentafluorophenyl)borate,

1,1'-dimethylferrocenium tetrakis(pentafluorophenyl)borate,

decamethylferrocenium tetrakis(pentafluorophenyl)borate,

acetylferrocenium tetrakis(pentafluorophenyl)borate,

formylferrocenium tetrakis(pentafluorophenyl)borate,

cyanoferrocenium tetrakis(pentafluorophenyl)borate,

silver tetrakis(pentafluorophenyl)borate,

trityltetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, sodiumtetrakis(pentafluorophenyl)borate,

tetraphenylporphyrin manganese tetra(pentafluorophenyl)borate,

tetra(pentafluorophenyl)boric acid (tetraphenylporphyrin iron chloride),

tetra(pentafluorophenyl)boric acid. (tetraphenylporphyrin zinc),

tetrafluorosilver borate, hexafluoroarsenical silver, andhexafluorosilver antimonate.

Further, compounds other than those represented by Formula (V) or (VI)such as tris(pentafluorophenyl)boron, tris (3,5-di(trifluoromethyl)phenyl)boron and triphenylboron, can be also used.

Organic aluminum compounds as Component (C) include those represented bythe following formula (VII), (VIII) or (IX):

    R.sup.12.sub.r AlQ.sub.3-r                                 (VII)

wherein R¹² is a hydrocarbon group such as an alkyl group, alkenylgroup, aryl group or arylalkyl group having 1 to 20, preferably 1 to 12carbon atoms; Q is a hydrogen atom, a C₁₋₂₀ alkoxy group or a halogenatom; and r is a number between 1 and 3.

Examples of compounds represented by Formula (VII) are, for example,trimethylaluminum, triethylaluminum, triisobutylaluminum,dimethylaluminum chloride, diethylaluminum chloride, methylaluminumdichloride, ethylaluminum dichloride, dimethylaluminum fluoride,diisobutylaluminum hydride, diethylaluminum hydride andethylaluminumsesquichloride.

Chain aluminoxanes represented by the following Formula (VIII): ##STR3##wherein R¹² is as defined in Formula (VII); and s is a degree ofpolymerization, usually from 3 to 50.

Cyclic alkylaluminoxanes having a repeating unit represented by theformula: ##STR4## wherein R¹² is defined in Formula (VII); and s is adegree of polymerization, usually from 3 to 50.

Of these compounds represented by Formulas (VII) to (IX), preferablecompounds are those represented by Formula (VII). Particularlypreferable compounds are those represented by Formula (VII) wherein r is3, more particularly, alkylaluminum such as trimethylaluminum,triethylaluminum or triisobutylaluminum.

Methods of preparing the above aluminoxanes are not particularly limitedto, but include any known methods such as a process comprisingcontacting alkylaluminum with a condensation agent such as water.Alkylaluminum and a condensation agent can be reacted by known methods,for example, (1) a method comprising dissolving an organoaluminumcompound in an organic solvent, and contacting the solution with water;.(2) a method comprising adding an organoaluminum compound to startingmaterials for polymerization, and adding water to the reaction mixturelater; (3) a method comprising reacting an organoaluminum compound withcrystalline water contained in a metal salt and the like or wateradsorbed to an inorganic material or an organic material; (4) a methodcomprising reacting tetraalkyldialuminoxane with trialkylaluminum, andthen reacting the reaction product with water.

Catalysts which can be used in the process of the present inventioncomprise, as main ingredients, the above Component (A) and Component(B), and optionally, Component (C).

In this case, the use conditions are not limited; however it ispreferable to adjust a ratio (molar ratio) of Component (A) to Component(B) to 1:0.01 to 1:100, more preferably 1:0.5 to 1:10, most preferably1:1 to 1:5. Further, reaction temperature may preferably range from-100° to 250° C. Reaction pressure and reaction time can beappropriately selected.

Further, the amount of Component (C) used may be from 0 to 2,000 mol,preferably from 5 to 1,000 mol, most preferably from 10 to 500 mol, per1 mol of Component (A). The use of Component (C) may improvepolymerization activity. However, the use of excess amount of Component(C) is not desirable since great amount of the organoaluminum compoundwill remain in the resultant polymer.

In addition, a way of using the catalysts is not particularly limited.For example, it is possible that Components (A) and (B) are preliminaryreacted and the reaction product is separated, washed and used forpolymerization. It is also possible that Components (A).and (B)themselves are contacted in a polymerization system. Further, Component(C) can be contacted with Component (A), Component (B), or the reactionproduct of Component (A) and Component (B). These components can becontacted before polymerization or during polymerization. Further, thesecomponents can be added to monomers or a solvent before polymerization,or to the polymerization system.

In the process of the present invention, a cyclic olefin can behomo-polymerized, or a cyclic olefin and an alpha-olefin can beco-polymerized in the presence of the above-mentioned catalysts.

As used herein, the cyclic olefins include cyclic monoolefins having onedouble bond and cyclic diolefins having two double bonds.

The cyclic monoolefins include, for example, monocyclic olefins such ascyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene;substituted monocyclic olefins such as 3-methylcyclopentene and3-methylcyclohexene; polycyclic olefins such as norbornene,1,2-dihydrodicyclopentadiene and1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene; andsubstituted polycyclic olefins such as 1-methylnorbornene,5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene,5-phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene,5-vinylnorbornene, 5-chloronorbornene, 5-fluoronorbornene,5-chloromethylnorbornene, 5-methoxynorbornene, 7-methylnorbornene,5,6-dimethylnorbornene, 5,5-dichloronorbornene,5,5,6-trimethylnorbornene, 5,5,6-trifluoro-6-trifluoromethylnorbornene,2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene and2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene.

Of these compounds, preferred are polycyclic olefins, particularlynorbornene or derivatives thereof.

Further, the cyclic diolefins are not particularly limited to, butinclude norbornadienes represented by the following formula (X):##STR5## wherein R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷ and R¹⁸ may be the same as ordifferent from each other, and are independently a hydrogen atom, aC₁₋₂₀ alkyl group or a halogen atom.

The norbornadienes represented by the above Formula (X) include, forexample, norbornadiene, 2-methyl-2,5-norbornadiene,2-ethyl-2,5-norbornadiene, 2-propyl-2,5-norbornadiene,2-butyl-2,5-norbornadiene, 2-pentyl-2,5-norbornadiene,2-hexyl-2,5-norbornadiene, 2-chloro-2,5-norbornadiene,2-bromo-2,5-norbornadiene, 2-fluoro-2,5-norbornadiene,7,7-dimethyl-2,5-norbornadiene, 7,7-methylethyl-2,5-norbornadiene,7,7-dichloro-2,5-norbornadiene, 1-methyl-2,5-norbornadiene,1-ethyl-2,5-norbornadiene, 1-propyl-2,5-norbornadiene,1-butyl-2,5-norbornadiene, 1-chloro-2,5-norbornadiene,1-bromo-2,5-norbornadiene, 7-methyl-2,5-norbornadiene,7-ethyl-2,5-norbornadiene, 7-propyl-2,5-norbornadiene,7-chloro-2,5-norbornadiene, 2,3-dimethyl-2,5-norbornadiene,1,4-dimethyl-2,5-norbornadiene and1,2,3,4-tetramethyl-2,5-norbornadiene.

Further, suitable alpha-olefins to be co-polymerized with a cyclicolefin include, for example, those having 2 to 25 carbon atoms such asethylene, propylene, butene-1 and 4-methylpentene-1. Of these, ethyleneis most preferable.

Further, in the process of the present invention, as desired,copolymerizable unsaturated monomer components other than the abovecompounds, can be used. Unsaturated monomers which can be optionallycopolymerized include, for example, alpha-olefins other than thoselisted above, cyclic olefins other than those listed above, and chaindienes Such as butadiene, isoprene and 1,5-hexadiene.

As for polymerization conditions, the polymerization temperature mayrange from -100° to 250° C., preferably from -50° to 200° C. Further,the catalyst is preferably used in an amount to provide a startingmonomer/Component (A) molar ratio or a starting monomer/Component (B)molar ratio of from 1 to 10⁹, preferably from 100 to 10⁷. Thepolymerization time may usually range from 1 minute to 10 hours. Thereaction pressure may range from normal pressure to 100 Kg/cm² G,preferably from normal pressure to 50 Kg/cm² G.

Polymerization methods are not particularly limited to, but include bulkpolymerization, solution polymerization and suspension polymerization.

In the case of using polymerization solvents, suitable solvents includearomatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene;alicyclic hydrocarbons such as cyclopentane, cyclohexane andmethylcyclohexane; aliphatic hydrocarbons such as pentane, hexane,heptane and octane; and halogenated hydrocarbons such as chloroform anddichloromethane. These solvents can be used alone or in combination.Monomers such as alpha-olefins can also be used as solvent.

The molecular weight of the resultant polymer can be controlled byappropriately selecting the amount of each catalyst component andpolymerization temperature, or by a polymerization reaction in thepresence of hydrogen.

In the case of preparation of cyclic olefin/alpha-olefin copolymers inaccordance with the process of the present invention, substantiallylinear, random copolymers having a ratio of a structural unit derivedfrom alpha-olefin to a structural unit derived from cyclic olefin, of0.1:99.9 to 99.9 to 0.1. It is possible to confirm, by completelydissolving the resultant copolymer in Decalin at 135° C., that thecopolymers are substantially linear. In this case, in general,copolymers having an intrinsic viscosity of 0.01 to 20 dl/g, measured inDecalin at 135° C., can be obtained.

Cyclic Olefin Copolymers (I):

The cyclic olefin copolymers (I) of the present invention have (1) 0.1to 40 mol % of the repeating unit of the formula [X] and 60 to 99.9 mol% of the repeating unit of the formula [Y]; (2) an intrinsic viscosityof 0.01 to 20 dl/g; and (3) a glass transition temperature (Tg) of 150to 370° C.

In the repeating unit represented by the general Formula [X], R^(a) is ahydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.

As used herein, the hydrocarbon groups having 1 to 20 carbon atomsinclude, for example, a methyl group, ethyl group, isopropyl group,isobutyl group, n-butyl group, n-hexyl group, octyl group and octadecylgroup.

Alpha-olefins which can provide the repeating unit represented by thegeneral Formula [X] include, for example, ethylene, propylene, 1-butene,3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, decene andeicosene.

In the repeating units represented by the general Formula [Y], R^(b) toR^(m) are independently a hydrogen atom, a hydrocarbon group having 1 to20 carbon atoms, or a substituent having a halogen atom, oxygen atom ornitrogen atom.

As used herein, the hydrocarbon groups having 1 to 20 carbon atomsinclude, for example, alkyl groups having 1 to 20 carbon atoms such as amethyl group, ethyl group, n-propyl group, isopropyl group, n-butylgroup, isobutyl group, tert.-butyl group and hexyl group; aryl groups,alkylaryl groups or arylalkyl groups having 6 to 20 carbon atoms such asa phenyl group, tolyl group and benzyl group; alkylidene groups having 1to 20 carbon atoms such as a methylidene group, ethylidene group andpropylidene group; alkenyl groups having 2 to 20 carbon atoms such as avinyl group and allyl group. However, R^(b), R^(c), R^(f) and R^(g)cannot be an alkylidene group. In addition, if any one of R^(d), R^(e)and R^(h) to R^(m) is an alkylidene group, a carbon atom to which thealkylidene group is attached, will not have the other substituent.

Further, the halogen-containing substituents include, for example,halogen groups such as fluorine, chlorine, bromine and iodine;halogenated alkyl groups having 1 to 20 carbon atoms such as achloromethyl group, bromomethyl group and chloroethyl group.

The oxygen-containing substituents include, for example, alkoxy groupshaving 1 to 20 carbon atoms such as a methoxy group, ethoxy group,propoxy group and phenoxy group; and alkoxycarbonyl groups having 1 to20 carbon atoms such as a methoxycarbonyl group and ethoxycarbonylgroup.

The nitrogen-containing substituents include, for example, alkylaminogroups having 1 to 20 carbon atoms such as a dimethylamino group anddiethylamino group; and cyano groups.

Examples of cyclic olefins which can provide the repeating unitsrepresented by the general formula [Y] include: norbornene,5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene,5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene,5,5,6-trimethylnorbornene, 5-phenylnorbornene, 5-benzylnorbornene,5-ethylidenenorbornene, 5-vinylnorbornene,1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-ethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2,3-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-hexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8, 8a-octahydronaphthalene,2-ethylidene-1,4,5,8-dimethano-1,2,3,4, 4a,5,8,8a-octahydronaphthalene,2-fluoro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,1,5-dimethyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-cyclohexyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a -octahydronaphthalene,2,3-dichloro-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,2-isobutyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene,1,2-dihydrodicyclopentadiene, 5-chloronorbornene,5,5-dichloronorbornene, 5-fluoronorbornene,5,5,6-trifluoro-6-trifluoromethylnorbornene, 5-chloromethylnorbornene,5-methoxynorbornene, 5,6-dicarboxylnorbornene anhydrate,5-dimethylaminonorbornene and 5-cyanonorbornene.

The cyclic olefin copolymers (I) of the present invention are basicallycomposed of the above-mentioned alpha-olefin components and cyclicolefin components. However, as far as the objects of the presentinvention can be achieved, the other copolymerizable unsaturated monomercomponents can be included if desired.

Such unsaturated monomers which can be optionally copolymerized include(1) alpha-olefins which are listed before, but not used as maincomponent; (2) cyclic olefins which are listed before, but not used asmain component; (3) cyclic diolefins such as dicyclopentadiene andnorbornadiene; (4) chain diolefins such as butadiene, isoprene and1,5-hexadiene; and (5) monocyclic olefins such as cyclopentene andcycloheptene.

The cyclic olefin copolymers (I) of the present invention may have aratio of repeating unite [X] content (x mol %) to repeating unit [Y]content (y mol %) of 0.1 to 40:99.9 to 60, preferably 0.3 to 38:99.7 to62, most preferably 10 to 35:90 to 65. If the repeating unit [X] contentis less than 0.1 mol %, the resultant copolymer will have poorflowability. If the repeating unit [X] content exceeds 40 mol %, theresultant copolymer will have insufficient heat resistance.

The cyclic olefin copolymers (I) of the present invention have anintrinsic viscosity measured at 135° C. in decaline of 0.01 to 20 dl/g.If the intrinisic viscosity is less than 0.01 dl/g, the strength of theresultant copolymer will be remarkably decreased. If the intrinsicviscosity exceeds 20 dl/g, the copolymer will have remarkably poormoldability. More preferable intrinsic viscosity may be 0.05 to 10 dl/g.

Further, the cyclic olefin copolymers (I) of the present invention havea glass transition temperature (Tg) of 150° to 370° C., preferably 160°to 350° C., most preferably 170° to 330° C. If such copolymers havingglass transition temperature within these ranges are used, the resultantfilms or sheets can be effectively used at low temperature. The glasstransition temperature (Tg) can be controlled by changing the componentratio of the copolymer and the kind of the monomers used, depending uponthe intended application and required physical properties therefor.

The cyclic olefin copolymers (I) of the present invention can becomposed of a copolymer having the above-mentioned physical propertiesand also can be composed of such copolymer and a copolymer havingphysical properties outside of the above ranges. In the latter case, thecomposition should have the physical properties within the above ranges.

Cyclic Olefin Copolymers (II):

The cyclic olefin copolymers (II) of the present invention have (1) 80to 99.9 mol % of the repeating unit of the formula [X] and 0.1 to 20 mol% of the repeating unit of the formula [Y]; (2) an intrinsic viscosityof 0.01 to 20 dl/g; (3) a glass transition temperature (Tg) of less than30° C; and (4) a tensile modulus of less than 2,000 Kg/cm².

Further, as characteristic feature, the cyclic olefin copolymers (II)have a melt peak measured by DSC of less than 90° C. The cyclic olefincopolymers (II) also show a crystallization peak measured by DSC (heatdown stage) such that the sub peak appears on the high temperature sideagainst the main peak.

In the cyclic olefin copolymers (II) of the present invention, therepeating unit represented by the general Formula [X] or [Y], andunsaturated monomers which can be optionally copolymerized, are the sameas those described for the cyclic olefin copolymers (I).

The cyclic olefin copolymers (II) of the present invention may have aratio of repeating unit [X] content (x mol %) to repeating unit [Y]content (y mol %) of 80 to 99.9:20 to 0.1, preferably 82 to 99.5:18 to0.5, most preferably 85 to 98:15 to 2. If the repeating unit [X] contentis less than 80 mol %, the resultant copolymer will have high glasstransition temperature and high tensile modulus, resulting in films orsheets having a poor elongation recovery property, and articles madewith a mold having poor impact strength and poor elasity. On the otherhand, if the repeating unit [X] content exceeds 99.9 mol %, meritoriouseffects derived from introduction of the cyclic olefin component willnot be satisfactory.

It is preferable that the cyclic olefin copolymers (II) be substantiallylinear copolymers having no gel cross-linking structure in which therepeating units [X] and [Y] are randomly arranged. It can be confirmedby complete dissolution of a copolymer in Decalin at 135° C. that thecopolymer does not have a gel cross-linking structure.

The cyclic olefin copolymers (II) of the present invention have anintrinsic viscosity measured in decalin at 135° C. of 0.01 to 20 dl/g.If the intrinsic viscosity is less than 0.01 dl/g, the strength of theresultant copolymer will be remarkably decreased. If the intrinsicviscosity exceeds 20 dl/g, the copolymer will have remarkably poormoldability. More preferable intrinsic viscosity may be 0.05 to 10 dl/g.

The molecular weight of the cyclic olefin copolymers (II) is notparticularly limited. However, the cyclic olefin copolymers (II) havepreferably a weight average molecular weight (Mw) measured by gelpermeation chromatography (GPC) of 1,000 to 2,000,000, more preferably5,000 to 1,000,000; a number average molecular weight (Mn) of 500 to1,000,000, more preferably 2,000 to 800,000; and a molecular weightdistribution (Mw/Mn) of 1.3 to 4, more preferably 1.4 to 3. Copolymershaving a molecular weight distribution of greater than 4, have highcontent of low molecular weight components, resulting in that theresultant molded article made with a mold and films may become sticky.

The cyclic olefin copolymers (II) of the present invention have a glasstransition temperature (Tg) of less than 30° C. If such copolymershaving glass transition temperature within these ranges are used, theresultant films or sheets can be effectively used at low temperature.More preferred glass transition temperature (Tg) is less than 20° C.,particularly less than 15° C. The glass transition temperature (Tg) canbe controlled by changing the component ratio of the copolymer and thekind of the monomers used, depending upon the intended application andrequired physical properties therefor.

Further, the cyclic olefin copolymers (II) of the present inventionpreferably have a crystallization degree measured by X-raydiffractiometry of less than 40%. If the crystallization degree exceeds40%, the elongation recovery property and transparency may be decreased.More preferred crystallization degree is less than 30%, particularlyless than 25%.

The cyclic olefin copolymers (II) of the present invention should have atensile modulus of less than 2,000 Kg/cm². For example, if the copolymerhaving a tensile strength of not less than 2,000 Kg/cm² is used toprepare a film for packaging, a great amount of energy will be requiredduring packaging and beautiful packaging corresponding to an item to bepackaged cannot be obtained. If such copolymer is used to prepare anarticle made with a mold, the resultant product may have insufficientimpact strengths. More preferred impact strength is 50 to 1,500 Kg/cm².

Further, the cyclic olefin copolymers (II) of the present inventionpreferably show a broad melt peak measured by DSC at lower than 90° C.The copolymer having a sharp melt peak at 90° C. or higher hasinsufficient random arrangement of a cyclic olefin component and analpha-olefin component, resulting in poor elongation recovery propertywhen molded into a film or the like. In addition, the broad peak ispreferably seen within a range of 10° to 85° C.

In the DSC measurement, the cyclic olefin copolymers (II) of the presentinvention do not exhibit a sharp melt peak. In particular, those havinglow crystallization degree exhibit almost no peaks at the measurementconditions for conventional polyethylene.

Further, the cyclic olefin copolymers (II) of the present inventionpreferably exhibit crystallization peaks measured by DSC (temperaturedecrease measurement) such that at least one relatively small sub peakappears on the high temperature side against the main peak.

Because of these good thermal properties in addition to theabove-mentioned physical properties of the molded articles, includingbroad range of molding temperature, high quality molded articles such asfilms can be stably produced.

The cyclic olefin copolymers (II) of the present invention can becomposed of a copolymer having the above-mentioned physical propertiesand also can be composed of such copolymer and a copolymer havingphysical properties outside of the above ranges. In the latter case, thecomposition should have the physical properties within the above ranges.

Cyclic Olefin Copolymer Compositions:

The first cyclic olefin copolymer compositions comprise (a) 100 parts byweight of a cyclic olefin copolymer (II) and (b) 0.01 to 10 parts byweight of an anti-blocking agent and/or a lubricant. The second cyclicolefin copolymer compositions further comprise (c) 1 to 100 parts byweight of an alpha-olefin based polymer in addition to Components (a)and (b).

In the cyclic olefin copolymer compositions of the present invention,anti-blocking agents, Component (b) are not particularly limited to, butinclude, for example, oxides, fluorides, nitrides, sulfates, phosphatesand carbonates of metals, and double salts thereof. More specifically,the anti-blocking agents include, for example, silicon oxide, titaniumoxide, zirconium oxide, aluminum oxide, aluminosilicate, zeolite,diatomaceous earth, talc, kaolinite, sericite, montmorillonite,hectolite, calcium fluoride, magnesium fluoride, boron nitride, aluminumnitride, calcium sulfate, strontium sulfate, barium sulfate, calciumphosphate, strontium carbonate, barium phosphate, calcium carbonate,strontium carbonate and barium carbonate.

Further, lubricants which can be used as Component (b) are also notparticularly limited to, but include higher aliphatic hydrocarbons,higher fatty acids, fatty acid amides, fatty acid esters, fatty acidalcohols, polyhydric alcohols and the like. These lubricants can be usedalone or in combination.

More specifically, suitable lubricants include, for example, liquidparaffin, natural paraffin polyethylene wax, fluorocarbon oil, lauricacid, palmitic acid, stearic acid, isostearic acid, hydroxylauric acid,hydroxystearic acid, oleic acid amide, lauric acid amide, erucic acidamide, methyl stearate, butyl stearate, stearyl alcohol, cetyl alcohol,isocetyl alcohol, ethylene glycol, diethylene glycol and fatty acidmonoglyceride.

In addition, it is possible to use the anti-blocking agent alone, thelubricant alone or combinations thereof.

In the cyclic olefin copolymer compositions, alpha-olefin basedpolymers, Component (c) are homopolymers or copolymers prepared from, asone component, an alpha-olefin represented by the following generalformula:

    CH.sub.2 ═CHR.sup.13

wherein R¹³ is a hydrogen atom or an alkyl group having 1 to 20 carbonatoms, provided that the cyclic olefin copolymers (II), theabove-mentioned Component (a) are excluded.

More specifically, suitable alpha-olefin based polymers, Component (c)include, for example, polyethylene, an ethylene/1-butene copolymer, anethylene/4-methyl-1-pentene copolymer, an ethylene/1-hexene copolymer,an ethylene/1-octene copolymer, an ethylene/vinyl acetate copolymer, anethylene/acrylic acid copolymer, its metal salt, polypropylene, apropylene/ethylene copolymer, a propylene/1-butene copolymer, apoly-1-butene/ethylene copolymer, a 1-butene/propylene copolymer, a1-butene/4-methyl-1-pentene copolymer, a poly-4-methyl-1-pentene,poly-3-methyl-1-butene. Of these polymers, polyethylene, anethylene/1-butene copolymer, an ethylene/1-hexene copolymer and anethylene/1-octene copolymer are more suitable.

The above first compositions comprise 0.01 to 10 parts by weight,preferably 0.02 to 8 parts by weight, more preferably 0.05 to 5 parts byweight of an anti-blocking agent and/or a lubricant, Component (b),based on 100 parts by weight of the cyclic olefin copolymer (II),Component (a).

The above second composition further comprise 1 to 100, preferably 2 to80, more preferably 3 to 50 parts by weight of an alpha-olefin basedpolymer, Component (c), based on 100 parts by weight of the cyclicolefin copolymer (II), Component (a) in addition to the anti-blockingagent and/or the lubricant, Component (b). In the second compositions,the addition of the alpha-olefin based polymer, Component (c) can makeit possible to reduce the amount of Component (b) used and can alsosolve problems such as bleeding out.

In the first and second compositions, if the amount of Component (b)added is less than 0.01 parts by weight, the compositions will have toolarge adhesiveness, resulting in poor moldability. If the amount exceeds10 parts by weight, the transparency will be decreased.

Further, in the second compositions, if the amount of Component (c)added is less than 1 part by weight, the meritorious effects derivedfrom addition of the alpha-olefin polymer cannot be expected. If theamount exceeds 100 parts by weight, the elongation recovery propertywill be insufficient. In addition, the cyclic olefin copolymercompositions of the present invention may comprise the other additivessuch as stabilizers such as an antioxidant and UV-absorbant, antistaticagent, inorganic or organic filler, dye, pigment and the like.

There is no specific limitation to a production process of the cyclicolefin copolymer compositions of the present invention. However, thecompositions can be effectively produced by mixing each of components ina molten state. Conventional melt-mixing machines which can be usedinclude, for example, open type ones such as a mixing roll and closedtype ones such as a Bunbury mixer, extruder, kneader, continuous mixerand the like.

In addition, it is also preferable to add additives such as Component(b) to the compositions, by preliminarily add such additives to a cyclicolefin copolymer or an alpha-olefin based resin to prepare a masterbatch.

Molded Articles:

The cyclic olefin copolymers (I) and (II), and the cyclic olefincopolymer compositions of the present invention can be molded intofilms, sheets and other various molded articles by known methods. Forexample, the cyclic olefin copolymers or compositions can be subjectedto extrusion molding, injection molding, blow molding or rotationmolding with use of a uniaxial extruder, vent type extruder, biaxialscrew extruder, biaxial conical screw extruder, cokneader, pratificater,mixtruder, planetary screw extruder, gear type extruder, screwlessextruder or the like. Further, films and sheets can be produced by aT-die method, inflation method or the like.

In addition, the cyclic olefin copolymer compositions of the presentinvention can be directly subjected to processing during the productionof the composition if necessary. In the practice of processing, knownadditives such as heat stabilizer, light stabilizer, antistatic agent,slipping agent, anti-blocking agent, deodorant, lubricant, synthesizedoil, natural oil, inorganic or organic filler, dye and pigment, can beadded if desired.

The films or sheets obtained from the cyclic olefin copolymers (I) ofthe present invention as described above are superior in heatresistance, transparency, strength and hardness, and thus can beeffectively used in an optical, medical, and food field or the like.

The films or sheets made form the cyclic olefin copolymers (II) of thepresent invention have a good elongation recovery property, goodtransparency, suitable elasticity and well-balanced physical properties,and thus can be effectively used in a packaging, medical, agriculturalfield or the like.

Further, the wrapping films made of the cyclic olefin copolymers (II) ofthe present invention are superior in various properties such astransparency, an elongation recovery property, adhesiveness, a tensileproperty, stabbing strength, tear strength, low temperature heatsealability. The wrapping films have no problems from a food sanitaryview point and from a waste incineration view point, and thus arepollutionless products.

Furthermore, the molded articles made with a mold from the cyclic olefincopolymers (II) have good transparency, elasticity and impact strength,and thus can be used as various products such as automotive parts, partsfor home electronics appliances, electric wire coating parts, goods ormaterials for construction.

EXAMPLES

The present invention will be described in more detail with reference tothe following Examples and Comparative Examples, which are not construedas limiting.

In the Examples and Comparative Examples, physical properties weremeasured as follows.

Mw, Mn, Mw/Mn

In Examples 1 to 73, the weight average molecular weight (Mw), numberaverage molecular weight (Mn) and molecular weight distribution (Mw/Mn)were measured with GPC-880 manufactured by Nihon Bunkoh (column: TSKGMH-6×1 manufactured by Tosoh; GL-A120×1 and GL-A130×1 manufactured byHitachi) under the following conditions:

Solvent: Chloroform

Temperature: 23° C.

Standard Polymer: Polystyrene.

In the other Examples and Comparative Examples, Mw, Mn, and Mw/Mn weremeasured with ALC/GPC-150C manufactured by Waters (column: TSK GMH-6×2manufactured by Tosoh) under the following conditions:

Solvent: 1,2,4-trichlorobenzene

Temperature: 135° C.

Standard Polymer: Polyethylene.

Intrinsic Viscosity [η]

The intrinsic viscosity was measured in decalin at 135° C.

Norbornene Content

The norbornene content was calculated from a ratio of the sum of a peakmeasured by ¹³ C-NMR appearing at 30 ppm and derived from ethylene and apeak derived from a methylene group in the 5th and 6th positions of thenorbornene; to a peak appearing at 32.5 ppm and derived from a methylenegroup in the 7th position of the norbornene.

Degree of Crystallization

A specimen was prepared by heat pressing. The specimen was evaluated atroom temperature by X-ray diffractiometry.

Glass Transition Temperature (Tg)

As a measurement equipment, VIBRON II-EA manufactured by Toyo Bowldingwas used. A specimen having a width of 4 mm, a length of 40 mm and athickness of 0.1 mm was evaluated at a heat up rate of 3° C./min. and ata frequency of 3.5 Hz. The glass transition temperature was calculatedfrom the peak of the loss modulus (E") measured in the above manner.

Softening Point

A copolymer was heated to 250° C. to prepare a press sheet having athickness of 0.1 mm. A specimen was cut out of the press sheet, andevaluated for softening point (TMA). The TMA is the temperature when thespecimen was torn off by heating the specimen at a heat up rate of 10°C./min while a load of 3 g/mm² was applied to the specimen. The TMA wasmeasured by TMA-100 manufactured by Seiko Electronics.

Melting Point (Tm)

The melting point was measured with DSC (7 series manufactured byPerkin-Elmer) at a heat up rate of 10° C./min. The melting point wasmeasured at between -50° C. and 150° C.

Crystallization Temperature

The crystallization temperature was measured by heating a specimen withDSC (7 series manufactured by Perkin-Elmer) at a heat up rate of 10°C/min. up to 150° C., keeping it for 60 seconds, and then cooling it ata heat down rate of 10° C./min. up to -50° C.

Tensile Modulus

The tensile modulus was measured with an autograph in accordance withJIS-K7113.

Tensile Strength at Break

The tensile strength at break was measured with an autograph inaccordance with JIS-K7113.

Elongation at Break

The elongation at break was measured with an autograph in accordancewith JIS-K7113.

Elastic Recovery

A specimen having a width of 6 mm and a length between clamps (L₀) of 50mm, was extended up to 150% with an autograph at a pulling rate of62mm/min., and kept for 5 minutes. Then, the specimen was allowed toshrink without rebounding. One minute later, the length between clamps(L₁) was measured. The elastic recovery was calculated in accordancewith the following equation.

    Elastic Recovery=[1-{(L.sub.1 -L.sub.0)/L.sub.0 }]×100

In this case, preferable elongation-recovery rate may be at least 10%,more preferably at least 30%, most preferably at least 60%.

All Light Transmittance, Haze

The all light transmittance and haze were measured with a digital hazecomputer manufactured by Suga Testing Equipment in accordance withJIS-K7105.

Heat Seal Temperature

A specimen (4 cm×20 cm) was heat sealed by pressing the heat sealportion (10 mm×15 mm) at a pressure of 2 Kg/cm² for one second. Thirtyminutes later, the specimen was pulled to separate the heat seal portionat a pulling rate of 200 mm/min until the heat seal was broken. The heatseal temperature was the temperature when the strength to pull thespecimen reached 300g.

Elemendorf Tear Strength

The Elemendorf tear strength was measured in accordance with JIS-P8116.

Self Adhesiveness

The self adhesiveness was evaluated by observing if the films pressedtogether was separated after a certain period of time.

Stabbing Strength

The load when a specimen was stabbed with a needle having a tip radiusof 0.5 mm at a stabbing rate of 50 mm/min., was measured.

Izod Impact Strength

The izod impact strength was measured in accordance with JIS-K7110.

Molding Shrinkage Factor

Injection molding was carried out with a mold (70 mm×70 mm×20 mm) toprepare a molded article After the molded article was allowed to standat 23° C. for 24 hours, the shrinkage factor was measured by comparingthe size of the molded article with the size of the mold.

Gas Permeability.

The gas permeability was measured at 23° C. in accordance with Process A(differential pressure process) of JIS-K7126.

Moisture Permeability

The moisture permeability was measured at 40° C. at a comparativemoisture of 90% in accordance with the cup process (Conditions B) ofJIS-Z0208.

Olsen Stiffness

The olsen stiffness was measured in accordance with JIS-K7106.

Shore Hardness

The shore hardness was measured in accordance with JIS-K7215.

Example 1

(1) Preparation of Triethylammonium

Tetrakis(pentafluorophenyl)borate:

Pentafluorophenyllithium prepared from bromopentafluorobenzene (152mmol) and butyllithium (152 mmol), was reacted with 45 mmol of borontrichloride in hexane to obtain tris(pentafluorophenyl)boron as a whitesolid product. The obtained tris(pentafluorophenyl)boron (41 mmol) wasreacted with pentafluorophenyllithium (41 mmol) to isolate lithiumtetrakis(pentafluorophenyl)borate as a white solid product.

Further, lithium tetrakis(pentafluorophenyl)borate (16 mmol) was reactedwith triethylamine hydrochloride (16 mmol) in water to obtain 12.8 mmolof triethylammonium tetrakis(pentafluorophenyl)borate as a white solidproduct.

It was confirmed by ¹ H-NMR and ¹³ C-NMR that the reaction product wasthe target product.

    ______________________________________                                        .sup.1 H-NMR (THFd.sub.8):                                                    --CH.sub.3  1.31 ppm                                                          --CH.sub.2 --                                                                             3.27 ppm                                                          .sup.13 C-NMR:                                                                --C.sub.6 F.sub.5                                                                         150.7, 147.5, 140.7, 138.7, 137.4, 133.5 ppm                      --CH.sub.2 --                                                                             48.2 ppm                                                          --CH.sub.3  9.1 ppm                                                           ______________________________________                                    

(2) Preparation of Catalyst:

One milimol of (cyclopentadienyl)trimethylzirconium was reacted with 1mmol of triethylammonium tetrakis(pentafluorophenyl)borate in 50 ml oftoluene at room temperature for four hours. After the solvent wasremoved, the obtained solid product was washed with 20 ml of petroleumether, dried and dissolved in 50 ml of toluene to obtain a catalystsolution.

(3) Polymerization:

A 100 ml flask was charged with 25 mmol of cyclopentene, 0.05 mmol ofthe catalyst (as transition metal component), and 25 ml of toluene.Then, the reaction was carried out at 20° C. for 4 hours. The reactionproduct was placed into methanol and the precipitated white solidproduct was recovered by filtration. Then, the obtained product waswashed with methanol and dried. The yield was 0.61 g.

The polymerization activity was 0.13 Kg/gZr (12 Kg/mol-Zr). As a resultof molecular weight measurement by GPC, it was found that the obtainedproduct had a Mw of 8,200 and a Mw/Mn of 2.6.

Further, it was found by ¹ H-NMR that the obtained product did not showabsorption derived from a carbon-carbon double bond at 5.7 ppm, and byinfrared spectrophotometry that the obtained product was polymerizedwith keeping the rings therein.

Example 2

In a 100 ml flask, 25 mmol of cyclopentene, 0.05 mmol of(cyclopentadienyl)tribenzylzirconium, and 0.05 mmol of triethylammoniumtetrakis(pentafluorophenyl)borate were reacted in 50 ml of toluene at20° C. for 4 hours. Thereafter, the reaction mixture was placed into 100ml of methanol and the precipitated white solid product was recovered byfiltration. Then, the obtained product was washed with 50 ml ofmethanol, and dried under reduced pressure to obtain 0.58g of whitepowders.

The polymerization activity was 0.13 Kg/gZr (12 Kg/mol-Zr). As a resultof molecular weight measurement by GPC, it was found that the obtainedproduct had a Mw of 9,400 and a Mw/Mn of 2.6.

Example 3

In a 100 ml flask, 25 mmol of norbornene (in a 70 wt. % norbornenesolution containing the same solvent as that for polymerization; thisprocedure will follow throughout the examples and comparative examplesas described below), 0.05 mmol of(pentamethylcyclopentadienyl)trimethylzirconium, and 0.05 mmol oftriethylammonium tetrakis(pentafluorophenyl)borate were reacted, whilestirring, in 50 ml of toluene at 20° C. for 4 hours. Thereafter, thereaction mixture was placed into 100 ml of methanol. A white solidproduct was precipitated, recovered by filtration, and then dried toobtain 0.51 g of a solid product.

The polymerization activity was 0.11 Kg/gZr (10 Kg/mol-Zr). As a resultof molecular weight measurement by GPC, it was found that the obtainedproduct had a Mw of 12,000 and a Mw/Mn of 2.3.

Example 4

To a 500 ml glass vessel, 200 ml of dried toluene and 21 mmol ofnorbornene were charged and ethylene gas was purged at 50° C. for 10minutes. Thereafter, 0.05 mmol ofbis(cyclopentadienyl)dimethylzirconium, and 0.05 mmol oftriethylammonium tetrakis(pentafluorophenyl)borate were added to thereaction vessel to initiate the polymerization. After the polymerizationwas carried out at 50° C. for 1 hour, the polymerization was terminatedby addition of methanol. The reaction product was recovered byfiltration, and dried to obtain 1.8 g of a copolymer.

The polymerization activity was 0.39 Kg/gZr (36 Kg/mol-Zr). The obtainedproduct had an intrinsic viscosity of 1.38 dl/g and a norbornene contentof 12 mol %.

Example 5

(1) Preparation of Catalyst:

One millimole of ethylenebis(indenyl)dimethylzirconium was reacted with1 mmol of triethylammonium tetrakis(pentafluorophenyl)borate in 50 ml oftoluene at 20° C. for 4 hours. After the solvent was removed, theobtained solid product was washed with 20 ml of petroleum ether, driedand dissolved in 50 ml of toluene to obtain a catalyst solution.

(2) Polymerization:

A 100 ml flask was charged with 25 mmol of cyclopentene, 0.05 mmol ofthe catalyst (as transition metal component), and 25 ml of toluene.Then, the reaction mixture was reacted at 20° C. for 4 hours. Thereaction product was placed into methanol and the precipitate whitesolid product was recovered by filtration to obtain 0.84 g of a whitesolid product.

The polymerization activity was 0.18 Kg/gZr (16.8 Kg/mol-Zr). As aresult of molecular weight measurement by GPC, it was found that theobtained product had a Mw of 7,800 and a Mw/Mn of 2.8.

Further, it was found by ¹ H-NMR that the obtained product did not showabsorption derived from a carbon-carbon double bond at 5.7 ppm, and byinfrared spectrophotometry that the obtained product was polymerizedwith keeping the rings therein.

Example 6

In a 100 ml flask, 25 mmol of cyclopentene, 0.05 mmol ofethylenebis(indenyl)dimethylzirconium, and 0.05 mmol of triethylammoniumtetrakis(pentafluorophenyl)borate were reacted in 50 ml of toluene.After the reaction was carried out at 20° C. for 4 hours, the reactionproduct was placed into 100 ml of methanol. The precipitated white solidproduct was recovered by filtration, washed with 50 ml of methanol, anddried under reduced pressure to obtain 0.63 g of white solid powders.

The polymerization activity was 0.14 Kg/gZr (12.6 Kg/mol-Zr). As aresult of molecular weight measurement by GPC, it was found that theobtained product had a Mw of 9,000 and a Mw/Mn of 2.7.

Example 7

In a 100 ml flask, 25 mmol of norbornene, 0.05 mmol ofethylenebis(indenyl)dimethylzirconium, and 0.05 mmol of triethylammoniumtetrakis(pentafluorophenyl)borate were reacted in 50 ml of toluene.After, the reaction was carried out, while stirring, at 20° C. for 4hours, the reaction mixture was placed into 100 ml of methanol. A whitesolid product was precipitated, recovered by filtration, and dried toobtain 0.49 g of a solid product.

The polymerization activity was 0.11 Kg/gZr (9.8 Kg/mol-Zr). As a resultof molecular weight measurement by GPC, it was found that the obtainedproduct had a Mw of 10,500 and a Mw/Mn of 2.1.

Example 8

The procedures of Example 7 were repeated except that ferroceniumtetrakis(pentafluorophenyl)borate was used instead of triethylammoniumtetrakis(pentafluorophenyl)borate. The yield was 0.82 g.

The polymerization activity was 0.18 Kg/gZr (16.4 Kg/mol-Zr). As aresult of molecular weight measurement by GPC, it was found that theobtained product had a Mw of 9,800 and a Mw/Mn of 2.6.

Example 9

The procedures of Example 7 were repeated except that silvertetrakis(pentafluorophenyl)borate was used instead of triethylammoniumtetrakis(pentafluorophenyl)borate. The yield was 0.56 g.

The polymerization activity was 0.12 Kg/gZr (11.2 Kg/mol-Zr). As aresult of molecular weight measurement by GPC, it was found that theobtained product had a Mw of 8,900 and a Mw/Mn of 2.4.

Example 10

The procedures of Example 7 were repeated except that trityltetrakis(pentafluorophenyl)borate was used instead of triethylammoniumtetrakis(pentafluorophenyl)borate. The yield was 0.64 g.

The polymerization activity was 0.14 Kg/gZr (12.8 Kg/mol-Zr). As aresult of molecular weight measurement by GPC, it was found that theobtained product had a Mw of 9,100 and a Mw/Mn of 2.3.

Example 11

A glass vessel purged with argon, was charged with 100 ml of toluene, 25mmol of cyclopentene, 0.01 mmol of triethylammoniumtetrakis(pentafluorophenyl)borate, 0.2 mmol of triisobutylaluminum and0.01 mmol of ethylenebis(indenyl) dimethylzirconium. The reaction wascarried out at 20° C. for 1 hour, and terminated by placing the reactionmixture into methanol. The white solid product was recovered byfiltration, and dried to obtain 0.85 g of a white solid product.

The polymerization activity was 0.93 Kg/gZr (85 Kg/mol-Zr). As a resultof molecular weight measurement by GPC, it was found that the obtainedproduct had a Mw of 11,000 and a Mw/Mn of 2.3.

Example 12

To a 500 ml glass vessel, 200 ml of dried toluene and 25 mmol ofnorbornene were charged and ethylene gas was purged at 50° C. for 10minutes. Thereafter, 0.01 mmol of ethylenebis(indenyl)dimethylzirconiumand 0.01 mmol of triethylammonium tetrakis(pentafluorophenyl)borate wereadded to the reaction vessel to initiate the polymerization. After thepolymerization was carried out at 50° C. for 1 hour, the polymerizationwas terminated by addition of methanol. The reaction product wasrecovered by filtration, and dried to obtain 2.1 g of a copolymer.

The polymerization activity was 2.3 Kg/gZr (210 Kg/mol-Zr). The obtainedproduct had an intrinsic viscosity of 1.40 dl/g and a norbornene contentof 10 mol %.

Example 13

To a 500 ml glass flask, 200 ml of dried toluene, 21 mmol of norbornene,0.2 mmol of triisobutylaluminum, 0.01 mmol ofethylenebis(indenyl)dimethylzirconium, and 0.01 mmol of triethylammoniumtetrakis(pentafluorophenyl)borate were charged and kept at 50° C. for 10minutes. Thereafter, the polymerization was carried out for 1 hour whileintroducing ethylene gas. The polymerization was terminated by additionof methanol. The obtained copolymer was recovered by filtration, anddried to obtain 6.3 g of a solid product.

The polymerization activity was 6.9 Kg/gZr (630 Kg/mol-Zr). The obtainedproduct had an intrinsic viscosity of 2.15 dl/g and a norbornene contentof 8 mol %.

Example 14

To a 500 ml glass vessel, 200 ml of dried toluene and 25 mmol ofnorbornene were charged and ethylene gas was purged at 50° C. for 10minutes. Thereafter, 0.05 mmol ofdimethylsilylenebis(cyclopentadienyl)dimethylzirconium, and 0.05 mmol oftriethylammonium tetrakis(pentafluorophenyl)borate were added to thereaction vessel to initiate the polymerization. After the polymerizationwas carried out at 50° C. for 1 hour, the polymerization was terminatedby addition of methanol. The reaction product was recovered byfiltration, and dried to obtain 4.0 g of a copolymer.

The polymerization activity was 0.88 Kg/gZr (80 Kg/mol-Zr). The obtainedproduct had an intrinsic viscosity of 1.36 dl/g and a norbornene contentof 38 mol %.

Comparative Example 1

A glass vessel purged with argon, was charged with 100 ml of toluene, 25mmol of cyclopentene, 0.2 mmol of aluminoxane and 0.05 mmol ofethylenebis(indenyl)dichlorozirconium. The reaction was carried out at20° C. for 1 hour, but a polymer was not obtained.

Comparative Example 2

To a 500 ml glass vessel, 200 ml of dried toluene and 21 mmol ofnorbornene were charged and ethylene gas was purged at 50° C. for 10minutes. Thereafter, 0.2 mmol of aluminoxane and 1.25×10⁻² mol ofbis(cyclopentadienyl)dichlorozirconium were added to the reaction vesselto initiate the polymerization. The polymerization was carried out at20° C. for 1 hour, but a polymer was not obtained.

Comparative Example 3

A 500 ml glass flask was charged with 200 ml of dried toluene and 21mmol of norbornene. To the flask, 0.2 mmol of aluminoxane and 0.01 mmolof dimethylsilylenebis(cyclopentadienyl)dichlorozirconium were furtheradded, and the reaction mixture was kept at 50° C. for 10 minutes.Thereafter, the polymerization was carried out for 1 hour whileintroducing ethylene gas, but a polymer was not obtained.

Example 15

(1) Synthesis of [Cp₂ Fe][B(C₆ F₅)₄ ](in accordance with techniquesdescribed in Jolly, W. L. The Synthesis and Characterization ofInorganic Compounds; Prentice-Hall: Englewood Cliffs, N.J., 1970, P487):

Ferrocene (3.7 g, 20.0 mmol) was reacted with 40 ml of concentratedsulfuric acid at room temperature for one hour to obtain very dark bluesolution. The obtained solution was placed in 1 liter of water withagitation to obtain slightly dark blue solution. The obtained solutionwas added to 500 ml of an aqueous solution of Li[B(C₆ F₅)₄ ] (13.7 g,20.0 mmol: Synthesized in accordance with a process described in J.Organometal. Chem., 2 (1964) 245). The light blue precipitate was takenby filtration and then washed with 500 ml of water five times. Then, thewashed product was dried under reduced pressure to obtain 14.7 g (17mmol) of the target product, [ferroceniumtetrakis(pentafluorophenyl)borate.

(2) Polymerization:

A 1 litter autoclave was charged With 400 ml of dried toluene, 0.05 mmolof ferrocenium tetrakis(pentafluorophenyl)borate, 0.05 mmol ofbis(cyclopentadienyl)dimethylzirconium and 100 mmol of norbornene. Then,the polymerization was carried out at 50° C. at an ethylene pressure of5 Kg/cm² for 4 hours to obtain 5.3 g of a copolymer. The polymerizationactivity was 1.2 Kg/gZr.

The obtained copolymer had a norbornene content of 2 mol %; an intrinsicviscosity of 2.24 dl/g; and a crystallization degree of 8%.

Example 16

A 1 litter autoclave was charged with 400 ml of dried toluene, 0.6 mmolof triisobutylaluminum, 0.03 mmol of ferroceniumtetrakis(pentafluorophenyl)borate, 0.03 mmol ofbis(cyclopentadienyl)dimethylzirconium and 200 mmol of norbornene. Then,the polymerization was carried out at 50° C. at an ethylene pressure of5 Kg/cm² for 0.5 hours, and terminated by addition of methanol. Thereaction product was recovered by filtration, and dried to obtain 71 gof a copolymer. The polymerization activity was 26 Kg/gZr.

The obtained copolymer had a norbornene content of 7 mol %; an intrinsicviscosity of 2.10 dl/g; and a crystallization degree of 6%.

Example 17

The procedures of Example 16 were repeated except that1,1'-dimethylferrocenium tetrakis(pentafluorophenyl)borate was usedinstead of ferrocenium tetrakis(pentafluorophenyl)borate. As a result,64 g of a copolymer were obtained. The polymerization activity was 23Kg/gZr.

The obtained copolymer had a norbornene content of 7 mol %; an intrinsicviscosity of 1.72 dl/g; and a crystallization degree of 7%.

Example 18

The procedures of Example 16 were repeated except that dimethylaniliniumtetrakis(pentafluorophenyl)borate was used instead of ferroceniumtetrakis(pentafluorophenyl)borate, and the polymerization temperaturewas changed to 4 hours. As a result, 30 g of a copolymer were obtained.The polymerization activity was 11 Kg/gZr.

The obtained copolymer had a norbornene content of 7 mol %; an intrinsicviscosity of 1.54 dl/g; and a crystallization degree of 8%.

Example 19

A 1 litter autoclave was charged with 400 ml of dried toluene, 0.4 mmolof triisobutylaluminum, 0.02 mmol of 1,1'-dimethylferroceniumtetrakis(pentafluorophenyl)borate, 0.02 mmol ofbis(cyclopentadienyl)dimethylzirconium and 260 mmol of norbornene. Then,the polymerization was carried out at 50° C. at an ethylene pressure of5 Kg/cm² for 1 hour, to obtain 95 g of a copolymer. The polymerizationactivity was 52 Kg/gZr;

The obtained copolymer had a norbornene content of 7 mol %; an intrinsicviscosity of 1.69 dl/g; and a crystallization degree of 7%.

Example 20

The procedures of Example 16 were repeated except that the amount ofnorbornene added was changed to 250 mmol, and the polymerizationtemperature was changed to 70° C. As a result, 105 g of a copolymer wereobtained. The polymerization activity was 38 Kg/gZr.

The obtained copolymer had a norbornene content of 5 mol %; an intrinsicviscosity of 2.15 dl/g; and a crystallization degree of 8%.

Example 21

The procedures of Example 20 were repeated except that the amount ofnorbornene added was changed to 350 mmol. As a result, 63 g of acopolymer were obtained. The polymerization activity was 23 Kg/gZr.

The obtained copolymer had a norbornene content of 10 mol %; anintrinsic viscosity of 1.89 dl/g; and a crystallization degree of 5%.

Example 22

The procedures of Example 16 were repeated except thatbis(pentamethylcyclopentadienyl)dimethylzirconium was used instead ofbis(cyclopentadienyl)dimethylzirconium, and the polymerization time waschanged to 4 hours. As a result, 85 g of a copolymer were obtained. Thepolymerization activity was 31 Kg/gZr.

The obtained copolymer had a norbornene content of 4 mol %; an intrinsicviscosity of 2.32 dl/g; and a crystallization degree of 9%.

Example 23

The procedures of Example 16 were repeated except thatbis(cyclopentadienyl)dimethylhafnium was used instead ofbis(cyclopentadienyl)dimethylzirconium. As a result, 53 g of a copolymerwere obtained. The polymerization activity was 10 Kg/gZr.

The obtained copolymer had a norbornene content of 7 mol %; an intrinsicviscosity of 1.77 dl/g; and a crystallization degree of 7%.

Example 24

The procedures of Example 16 were repeated except thatbis(cyclopentadienyl)dibenzylzirconium was used instead ofbis(cyclopentadienyl)dimethylzirconium. As a result, 74 g of a copolymerwere obtained. The polymerization activity was 27 Kg/gZr.

The obtained copolymer had a norbornene content of 6 mol %; an intrinsicviscosity of 1.85 dl/g; and a crystallization degree of 8%.

Example 25

The procedures of Example 22 were repeated except thatdimethylsilylenebis(cyclopentadienyl)dimethylzirconium was used insteadof bis(pentamethylcyclopentadienyl)dimethylzirconium. As a result, 39 gof a copolymer were obtained. The polymerization activity was 14 Kg/gZr.

The obtained copolymer had a norbornene content of 72 mol %; anintrinsic viscosity of 2.11 dl/g; and a crystallization degree of 0%.

Comparative Example 4

The procedures of Example 15 were repeated except that ferroceniumtetrakis(pentafluorophenyl)borate was not used. As a result, a polymerwas not obtained.

Comparative Example 5

The procedures of Example 15 were repeated except thatbis(cyclopentadienyl)dimethylzirconium was not used. As a result, apolymer was not obtained.

Example 26

The procedures of Example 16 were repeated except thatbis(cyclopentadienyl)dimethoxyzirconium was used instead ofbis(cyclopentadienyl)dimethylzirconium. As a result, 46 g of a copolymerwere obtained. The polymerization activity was 17 Kg/gZr.

The obtained copolymer had a norbornene content of 7 mol %; an intrinsicviscosity of 2.74 dl/g; and a crystallization degree of 6%.

Example 27

A 1 liter autoclave was charged with 400 ml of dried toluene, 0.6 mmolof triisobutylaluminum and 0.015 mmol ofbis(cyclopentadienyl)dichlorozirconium. After agitation, 0.045 mmol offerrocenium tetrakis(pentafluorophenyl)borate and 200 mmol of norbornenewere added to the reaction mixture. The polymerization was carried outat 50° C. at an ethylene pressure of 5 Kg/cm² for 0.5 hours, to obtain65 g of a copolymer. The polymerization activity was 48 Kg/gZr.

The obtained copolymer had a norbornene content of 8 mol %; an intrinsicviscosity of 2.30 dl/g; and a crystallization degree of 5%.

Example 28

The procedures of Example 24 were repeated except thatbis(cyclopentadienyl)dibenzylzirconium and ferroceniumtetrakis(pentafluorophenyl)borate were used in an amount of 0.015 mmol,respectively. As a result, 84 g of a copolymer were obtained. Thepolymerization activity was 62 Kg/gZr.

The obtained copolymer had a norbornene content of 6 mol %; an intrinsicviscosity of 2.13 dl/g; and a crystallization degree of 6%.

Example 29

The procedures of Example 27 were repeated except thatbis(cyclopentadienyl)monochloromonohydridezirconium was used instead ofbis(cyclopentadienyl)dichlorozirconium. As a result, 62 g of a copolymerwere obtained. The polymerization activity was 45 Kg/gZr.

The obtained copolymer had a norbornene content of 8 mol %; an intrinsicviscosity of 2.34 dl/g; and a crystallization degree of 5%.

Example 30

The procedures of Example 16 were repeated except that(cyclopentadienyl)trimethylzirconium was used instead ofbis(cyclopentadienyl)dimethylzirconium. As a result, 68 g of a copolymerwere obtained. The polymerization activity was 25 Kg/gZr.

The obtained copolymer had a norbornene content of 7 mol %; an intrinsicviscosity of 2.22 dl/g; and a crystallization degree of 6%.

Example 31

The procedures of Example 22 were repeated except thattetrabenzylzirconium was used instead ofbis(pentamethylcyclopentadienyl)dimethylzirconium. As a result, 50 g ofa copolymer were obtained. The polymerization activity was 18 Kg/gZr.

The obtained copolymer had a norbornene content of 6 mol %; an intrinsicviscosity of 2.50 dl/g; and a crystallization degree of 8%.

Example 32

The procedures of Example 16 were repeated except that silvertetrakis(pentafluorophenyl)borate was used instead of ferroceniumtetrakis(pentafluorophenyl)borate. As a result, 48 g of a copolymer wereobtained. The polymerization activity was 18 Kg/gZr.

The obtained copolymer had a norbornene content of 7 mol %; an intrinsicviscosity of 1.94 dl/g; and a crystallization degree of 6%.

Example 33

The procedures of Example 16 were repeated except that 100 mmol of1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene was usedinstead of norbornene. As a result, 35 g of a copolymer were obtained.The polymerization activity was 13 Kg/gZr.

The obtained copolymer had a cyclic olefin content of 5 mol %; anintrinsic viscosity of 1.57 dl/g; and a crystallization degree of 9%.

Example 34

The procedures of Example 33 were repeated except thatdimethylsilylenebis(cyclopentadienyl)dimethylzirconium was used insteadof bis(cyclopentadienyl)dimethylzirconium, and the polymerization timewas changed to 4 hours. As a result, 14 g of a copolymer were obtained.The polymerization activity was 5 Kg/gZr.

The obtained copolymer had a cyclic olefin content of 39 mol %; anintrinsic viscosity of 1.61 dl/g; and a crystallization degree of 0%.

Example 35

A 1 liter autoclave was charged with 400 ml of dried toluene, 0.6 mmolof triisobutylaluminum, 0.03 mmol of ferroceniumtetrakis(pentafluorophenyl)borate, 0.03 mmol ofbis(cyclopentadienyl)dimethylzirconium and 230 mmol of norbornene. Then,propylene was introduced into the autoclave to keep a propylene pressureof 2 Kg/cm², and the polymerization was carried out at 50° C. for 1 hourwhile ethylene was continuously introduced so as to keep a totalpressure to 5 Kg/cm². As a result, 41 g of a copolymer were obtained.The polymerization activity was 15 Kg/gZr.

The obtained copolymer had a norbornene content of 7 mol %; an intrinsicviscosity of 1.47 dl/g; and a crystallization degree of 0%.

Example 36

A 1 liter autoclave was charged with 400 ml of dried toluene, 0.6 mmolof triisobutylaluminum, and 0.05 mmol ofbis(cyclopentadienyl)dichlorozirconium. After agitation, 0.01 mmol ofbenzyl(4-cyano)pyridinium tetrakis(pentafluorophenyl)borate and 200 mmolof norbornene were added. Then, the polymerization was carried out at90° C. at an ethylene pressure of 9 Kg/cm² for 0.5 hours, to obtain 33 gof a copolymer. The polymerization activity was 72 Kg/gZr.

The obtained copolymer had a norbornene content of 6 mol %; and anintrinsic viscosity of 2.01 dl/g.

Example 37

The procedures of Example 36 were repeated except thatmethyl(2-cyano)pyridinium tetrakis(pentafluorophenyl)borate was usedinstead of benzyl(4-cyano)pyridinium tetrakis(pentafluorophenyl)borate.As a result, 15 g of a copolymer were obtained. The polymerizationactivity was 33 Kg/gZr.

The obtained copolymer had a norbornene content of 5 mol %; and anintrinsic viscosity of 2.34 dl/g.

Example 38

The procedures of Example 36 were repeated except thattetraphenylporphyrin manganese tetrakis(pentafluorophenyl)borate wasused instead of benzyl(4-cyano)pyridiniumtetrakis(pentafluorophenyl)borate. As a result, 58 g of a copolymer wereobtained. The polymerization activity was 127 Kg/gZr.

The obtained copolymer had a norbornene content of 6 mol %; and anintrinsic viscosity of 1.95 dl/g.

Example 39

A 1 liter autoclave was charged with 400 ml of dried hexane. Then, acatalyst solution prepared by pre-mixing 10 ml of toluene, 0.6 mmol oftriisobutylaluminum, and 0.06 mmol ofbis(cyclopentadienyl)dichlorozirconium and 0.006 mmol ofdimethylanilinium tetrakis(pentafluorophenyl)borate was added to theautoclave. After agitation, 200 mmol of norbornene was added. Then, thepolymerization was carried out at 90° C. at an ethylene pressure of 9Kg/cm² for 0.4 hours, to obtain 10 g of a copolymer. The polymerizationactivity was 18 Kg/gZr.

The obtained copolymer had a norbornene content of 16 mol %; and anintrinsic viscosity of 0.42 dl/g. Example 40

The procedures of Example 39 were repeated except that a mixed solventof 200 ml of hexane and 200 ml of toluene was used instead of 400 ml ofdried hexane. As a result, 59 g of a copolymer were obtained. Thepolymerization activity was 108 Kg/gZr.

The obtained copolymer had a norbornene content of 4.2 mol %; and anintrinsic viscosity of 1.14 dl/g.

Example 41

The procedures of Example 39 were repeated except that dried cyclohexanewas used instead of dried hexane, andbis(cyclopentadienyl)dichlorozirconium and dimethylaniliniumtetrakis(pentafluorophenyl)borate were used in an amount of 0.03 mmol,respectively. As a result, 67 g of a copolymer were obtained. Thepolymerization activity was 24 Kg/gZr.

The obtained copolymer had a norbornene content of 7.2 mol %; and anintrinsic viscosity of 1.26 dl/g.

Example 42

The procedures of Example 16 were repeated except thattrimethylaluminum, bis(cyclopentadienyl)dichlorozirconium anddimethylanilinium tetrakis(pentafluorophenyl)borate were used instead oftriisobutylaluminum, bis(cyclopentadienyl)dimethylzirconium andferrocenium tetrakis(pentafluorophenyl)borate, respectively. As aresult, 33 g of a copolymer were obtained. The polymerization activitywas 12 Kg/gZr.

The obtained copolymer had a norbornene content of 10 mol %; and anintrinsic viscosity of 2.00 dl/g.

Example 43

The procedures of Example 42 were repeated except that triethylaluminumwas used instead of trimethylaluminum. As a result, 17 g of a copolymerwere obtained. The polymerization activity was 6.2 Kg/gZr.

The obtained copolymer had a norbornene content of 10 mol %; and anintrinsic viscosity of 1.92 dl/g.

Example 44

A 1 liter autoclave was charged with 400 ml of dried toluene, 0.4 mmolof triisobutylaluminum, and 0.003 mmol ofbis(cyclopentadienyl)dichlorozirconium. After agitation, 0.006 mmol ofmethyldiphenylammonium tetrakis(pentafluorophenyl)borate and 260 mmol ofnorbornene were added. Then, the polymerization was carried out at 90°C. at an ethylene pressure of 6 Kg/cm² for 0.5 hours, to obtain 57 g ofa copolymer. The polymerization activity was 208 Kg/gZr.

The obtained copolymer had a norbornene content of 7.9 mol %; and anintrinsic viscosity of 1.13 dl/g.

Example 45

The procedures of Example 42 were repeated except that methylaluminoxanewas used instead of trimethylaluminum. As a result, 53 g of a copolymerwere obtained. The polymerization activity was 19 Kg/gZr.

The obtained copolymer had a norbornene content of 8 mol %; and anintrinsic viscosity of 1.83 dl/g.

Example 46

A 1 liter autoclave was charged with 400 ml of dried toluene, 0.6 mmolof triisobutylaluminum, and 0.002 mmol ofbis(cyclopentadienyl)dihydridezirconium. After agitation, 0.004 mmol ofdimethylanilinium tetrakis(pentafluorophenyl)borate and 200 mmol ofnorbornene were added. Then, the polymerization was carried out at 90°C. at an ethylene, pressure of 7 Kg/cm² for 0.5 hours, to obtain 48 g ofa copolymer. The polymerization activity was 263 Kg/gZr.

The obtained copolymer had a norbornene content of 4.7 mol %; and anintrinsic viscosity of 1.46 dl/g.

Example 47

The procedures of Example 42 were repeated except thattriisobutylaluminum was used instead of trimethylaluminum, andbis(cyclopentadienyl)dimethyltitanium was used instead ofbis(cyclopentadienyl)dichlorozirconium. As a result, 31 g of a copolymerwere obtained. The polymerization activity was 22 Kg/gTi.

The obtained copolymer had a norbornene content of 3.6 mol %; and anintrinsic viscosity of 1.83 dl/g.

Example 48

The procedures of Example 42 were repeated except thattriisobutylaluminum was used instead of trimethylaluminum, and5-methylnorbornene was used instead of norbornene. As a result, 38 g ofa copolymer were obtained. The polymerization activity was 14 Kg/gZr.

The obtained copolymer had a cyclic olefin content of 7 mol %; and anintrinsic viscosity of 1.97 dl/g.

Example 49

The procedures of Example 48 were repeated except that5-benzylnorbornene was used instead of 5-methylnorbornene. As a result,13 g of a copolymer were obtained. The polymerization activity was 4.8Kg/gZr.

The obtained copolymer had a cyclic olefin content of 11 mol %; and anintrinsic viscosity of 2.15 dl/g.

Example 50

The procedures of Example 42 were repeated except thattriisobutylaluminum was used instead of trimethylaluminum, and propylenewas used instead of ethylene. As a result, 17 g of a copolymer wereobtained. The polymerization activity was 6.2 Kg/gZr.

The obtained copolymer had a norbornene content of 6.4 mol %; and anintrinsic viscosity of 0.62 dl/g.

Example 51

A 1 liter autoclave was charged with 400 ml of dried toluene, 0.6 mmolof triisobutylaluminum, and 0.006 mmol ofbis(cyclopentadienyl)dichlorozirconium. After agitation, 0,006 mmol ofdimethylanilinium tetrakis(pentafluorophenyl)borate and 200 mmol ofnorbornene were added. Then, the polymerization was carried out at 70°C. at an ethylene pressure of 9.5 Kg/cm² for 0.5 hours, to obtain 53 gof a copolymer. The polymerization activity was 97 Kg/gZr.

The obtained copolymer had a norbornene content of 5 mol %; and anintrinsic viscosity of 1.43 dl/g.

Example 52

The procedures of Example 51 were repeated except that dimethylaniliniumtetrakis(pentafluorophenyl)borate was used in an amount of 0.012 mmol.As a result, 97 g of a copolymer were obtained. The polymerizationactivity was 177 Kg/gZr.

The obtained copolymer had a norbornene content of 5 mol %; and anintrinsic viscosity of 1.45 dl/g.

Example 53

The procedures of Example 51 were repeated except thattriisobutylaluminum was used in an amount of 1.8 mmol. As a result, 78 gof a copolymer were obtained. The polymerization activity was 143Kg/gZr.

The obtained copolymer had a norbornene content of 4 mol %; and anintrinsic viscosity of 1.67 dl/g.

Example 54

The procedures of Example 39 were repeated except that dimethylaniliniumtetrakis(pentafluorophenyl)borate was used in an amount of 0,012 mmol,and the polymerization was carried out at an ethylene pressure of 30g/cm² for 10 minutes. As a result, 78 g of a copolymer were obtained.The polymerization activity was 143 Kg/gZr.

The obtained copolymer had a norbornene content of 3 mol %; and anintrinsic viscosity of 1.39 dl/g.

Example 55

The procedures of Example 54 were repeated except that thepolymerization temperature was changed to 130° C. As a result, 12 g of acopolymer were obtained. The polymerization activity was 22 Kg/gZr.

The obtained copolymer had a norbornene content of 4 mol %; and anintrinsic viscosity of 1.65 dl/g.

Example 56

(1) Preparation of Catalyst Solution

A 2 liter glass vessel was charged with 500 ml of dried toluene, 10 mmolof triisobutylaluminum, 0.2 mmol ofbis(cyclopentadienyl)dichlorozirconium and 0.3 mmol of dimethylaniliniumtetrakis(pentafluorophenyl)borate, to obtain a catalyst solution.

(2) Continuous Polymerization

A 2 liter autoclave for continuous polymerization, was charged with 1liter of dried toluene, 90 ml of the catalyst solution prepared in Step(1) above and 360 mmol of norbornene. The polymerization was carried outat 90° C. at an ethylene pressure of 5 Kg/cm² for 0.5 hours. Thereafter,toluene, the catalyst solution and norbornene were supplied to theautoclave at a rate of 1 liter/hour, 90 ml/hour and 360 mmol/hour,respectively while the polymer solution was continuously taken out so asto keep the amount of the reaction mixture in the autoclave to 1 liter.Further, ethylene was also continuously supplied to the autoclave so asto keep the ethylene partial pressure to 5 Kg/cm² and the polymerizationtemperature was kept at 90° C. As a result, a copolymer was obtained ata production rate of 158 g/hours. The polymerization activity was 48Kg/gZr.

The obtained copolymer had a norbornene content of 5 mol %; and anintrinsic viscosity of 1.64 dl/g.

Example 57

A 500 ml flask was charged with 150 ml of dried toluene, 5 mmol oftriisobutylaluminum, and 0.025 mmol ofbis(cyclopentadienyl)dichlorozirconium. After agitation, 0.025 mmol ofdimethylanilinium tetrakis(pentafluorophenyl)borate and 50 mmol ofnorbornadiene were added. Then, the polymerization was carried out at25° C. for 3 hours while introducing ethylene at a rate of 30 l/hour, toobtain 0.35 g of a copolymer. The polymerization activity of 0.15Kg/gZr.

The obtained copolymer had a norbornene content of 45 mol %; and anintrinsic viscosity of 0.21 dl/g.

Example 58

The procedures of Example 50 were repeated except thatethylenebis(indenyl)dichlorozirconium was used instead ofbis(cyclopentadienyl)dichlorozirconium. As a result, 23 g of a copolymerwere obtained. The polymerization activity was 8 Kg/gZr.

The obtained copolymer had a norbornene content of 7 mol %; and anintrinsic viscosity of 0.76 dl/g.

Example 59

The procedures of Example 50 were repeated except thatisopropyl(cyclopentadienyl)(9-fluorenyl)dichlorozirconium was usedinstead of bis(cyclopentadienyl)dichlorozirconium. As a result, 21 g ofa copolymer were obtained. The polymerization activity was 8 Kg/gZr.

The obtained copolymer had a norbornene content of 6.8 mol %; and anintrinsic viscosity of 0.54 dl/g.

Example 60

A 1 liter autoclave was charged with 400 ml of dried toluene, 0.6 mmolof triisobutylaluminum, and 0.003 mmol ofbis(cyclopentadienyl)dichlorozirconium. After agitation, 0.006 mmol ofdimethylanilinium tetrakis(pentafluorophenyl)borate and 400 mmol ofnorbornene were added. Then, the polymerization was carried out at 90°C. at an ethylene pressure of 6 Kg/cm² and a hydrogen pressure of 2Kg/cm² for 0.5 hours, to obtain 8 g of a copolymer. The polymerizationactivity was 29 Kg/gZr.

The obtained copolymer had a norbornene content of 7 mol %; and anintrinsic viscosity of 0.06 dl/g.

Example 61

The procedures of Example 16 were repeated except that(cyclopentadienyl)trichlorozirconium was used instead ofbis(cyclopentadienyl)dimethylzirconium, and dimethylaniliniumtetrakis(pentafluorophenyl)borate was used instead of ferroceniumtetrakis(pentafluorophenyl)borate. As a result, 66 g of a copolymer wereobtained. The polymerization activity was 24 Kg/gZr.

The obtained copolymer had a norbornene content of 8 mol %; and anintrinsic viscosity of 2.34 dl/g.

Example 62

The procedures of Example 61 were repeated except that(pentamethylcyclopentadienyl)trichlorozirconium was used instead of(cyclopentadienyl)trichlorozirconium. As a result, 68 g of a copolymerwere obtained. The polymerization activity was 25 Kg/gZr.

The obtained copolymer had a norbornene content of 6 mol %; and anintrinsic viscosity of 2.51 dl/g.

Example 63

The procedures of Example 61 were repeated except that(pentamethylcyclopentadienyl)trimethylzirconium was used instead of(cyclopentadienyl)trichlorozirconium. As a result, 71 g of a copolymerwere obtained. The polymerization activity was 26 Kg/gZr.

The obtained copolymer had a norbornene content of 7 mol %; and anintrinsic viscosity of 2.47 dl/g.

Example 64

The procedures of Example 61 were repeated except that(pentamethylcyclopentadienyl)trimethoxyozirconium was used instead of(cyclopentadienyl)trichlorozirconium. As a result, 65 g of a copolymerwere obtained. The polymerization activity was 24 Kg/gZr.

The obtained copolymer had a norbornene content of 6.5 mol %; and anintrinsic viscosity of 2.68 dl/g.

Example 65

The procedures of Example 46 were repeated except that 0.002 mmol oftetrabenzylzirconium was used instead ofbis(cyclopentadienyl)dihydridezirconium. As a result, 62.7 g of acopolymer were obtained. The polymerization activity was 344 Kg/gZr.

The obtained copolymer had a norbornene content of 6.5 mol %; and anintrinsic viscosity of 1.76 dl/g.

Example 66

The procedures of Example 65 were repeated except that 0.002 mmol oftetrabutoxyzirconium was used instead of tetrabenzylzirconium. As aresult, 37.1 g of a copolymer were obtained. The polymerization activitywas 203 Kg/gZr.

The obtained copolymer had a norbornene content of 5.5 mol %; and anintrinsic viscosity of 1.89 dl/g.

Example 67

The procedures of Example 65 were repeated except that 0.002 mmol oftetrachlorozirconium was used instead of tetrabenzylzirconium. As aresult, 69.1 g of a copolymer were obtained. The polymerization activitywas 379 Kg/gZr.

The obtained copolymer had a norbornene content of 5.5 mol %; and anintrinsic viscosity of 1.71 dl/g.

Example 68

The procedures of Example 51 were repeated except thatbis(cyclopentadienyl)dimethylzirconium was used instead ofbis(cyclopentadienyl)dichlorozirconium, and tris(pentafluorophenyl)boronwas used instead of dimethylanilinium tetrakis(pentafluorophenyl)borate.As a result, 12 g of a copolymer were obtained. The polymerizationactivity was 22 Kg/gZr.

The obtained copolymer had a norbornene content of 8 mol %; and anintrinsic viscosity of 1.64 dl/g.

Example 69

A 1000 ml glass autoclave was charged with 500 ml of dried toluene, 10mmol of triisobutylaluminum, 0.25 mmol ofbis(cyclopentadienyl)dichlorozirconium and 0.25 mmol ofdimethylanilinium tetrakis(pentafluorophenyl)borate. After agitation, 1mol of norbornadiene was added. Then, the polymerization was carried outat 20° C. for 4 hours, to obtain 2.76 g of a copolymer. Thepolymerization activity was 0.12 Kg/gZr.

The obtained copolymer had a molecular weight (Mw) of 1,700 and amolecular weight distribution (Mw/Mn) of 2.83.

Comparative Example 6

A 1 liter autoclave, under nitrogen atmosphere was charged with 400 mlof toluene, 8 mmol of ethylaluminumsesquichloride (Al(C₂ H₅)₁.5 Cl₁.5),0.8 mmol of VO(OC₂ H₅)Cl₂ and 130 mmol of norbornene. The reactionmixture was heated to 40° C. and the reaction was carried out for 60minutes while continuously introducing ethylene so as to keep theethylene partial pressure to 3 Kg/cm². As a result, the yield was 6.16g. The polymerization activity was 0.15 Kg/gZr.

The obtained copolymer had a norbornene content of 12 mol %; and anintrinsic viscosity of 1.20 dl/g.

Example 70

The procedures of Example 34 were repeated except that the ethylenepressure was changed to 4 Kg/cm², and the polymerization temperature waschanged to 70° C. As a result, 17 g of a copolymer were obtained. Thepolymerization activity was 6.2 Kg / gZr.

The obtained copolymer had a norbornene content of 57 mol %; and anintrinsic viscosity of 1.47 dl/g.

Example 71

(1) Preparation of Triethylammonium

Tetrakis(pentafluorophenyl)borate:

Triethylammonium tetrakis(pentafluorophenyl)borate was prepared in thesame manner as in Example 1.

(2) Preparation of Catalyst:

One millimole of (cyclopentadienyl)trimethyltitanium was reacted with 1mmol of triethylammonium tetrakis(pentafluorophenyl)borate in 50 ml oftoluene at room temperature for 4 hours. After the solvent was removed,the obtained solid product was washed with 20 ml of petroleum ether,dried and dissolved in 50 ml of toluene to obtain a catalyst solution.

(3) Polymerization:

A 100 ml flask was charged with 25 mmol of norbornadiene, 0.05 mmol ofthe catalyst (as transition metal component), and 25 ml of toluene.Then, the reaction was carried out at 20° C. for 4 hours. The reactionproduct was placed into methanol and the precipitated white solidproduct was recovered by filtration. Then, the obtained product waswashed with methanol and dried. The yield was 0.41 g.

The obtained product had a polymerization activity of 170 g/gTi, and amolecular weight of 40,900. It was found that the obtained product wassoluble to conventional solvents such as toluene, chloroform andtetrahydrofuran.

It was also found by infrared spectrophotometry that the obtainedproduct showed strong absorption at 800cm⁻¹ which is derived from thefollowing structural unit (A). It was also found by ¹ H-NMR that theobtained product showed absorption derived from a carbon-carbon doublebond at 6.2 ppm, and did not show absorption derived from acarbon-carbon double bond contained in a polymer main chain at 5.3 ppm.Accordingly, it was confirmed that the obtained product had thefollowing structural units: ##STR6##

Example 72

In a 100 ml flask, 25 mmol of norbornadiene, 0.005 mmol of(cyclopentadienyl)tribenzyltitanium, and 0.005 mmol of triethylammoniumtetrakis(pentafluorophenyl)borate were reacted in 50 ml of toluene at20° C. for 4 hours. Thereafter, the reaction mixture was placed into 100ml of methanol and the precipitated white solid product was recovered byfiltration. Then, the obtained product was washed with 50 ml ofmethanol, and dried under reduced pressure to obtain 0.27 g of whitepowders. The polymerization activity was 1.1 Kg/gTi.

The obtained product had, a molecular weight (Mw) of 42,000.

Example 73

In a 100 ml flask, 25 mmol of norbornadiene, 0.005 mmol of(cyclopentadienyl)trimethyltitanium, 0.005 mmol of triethylammoniumtetrakis(pentafluorophenyl)borate and 0.1 mmol of triisobutylaluminum,were reacted in 50 ml of toluene. After agitation at 20° C. for 4 hours,the reaction mixture was placed into 100 ml of methanol. A white solidproduct was precipitated, recovered by filtration, and then dried toobtain 0.92 g of a solid product. The polymerization activity was 3.81Kg/gTi.

The obtained product had a molecular weight (Mw) of 61,000.

Example 74

In a 100 ml flask, 25 mmol of norbornadiene, 0.005 mmol of(pentamethylcyclopentadienyl)trimethyltitanium, 0,005 mmol oftriethylammonium tetrakis(pentafluorophenyl)borate and 0.1 mmol oftriisobutylaluminum, were reacted in 50 ml of toluene. After agitationat 20° C. for 4 hours, the reaction mixture was placed into 100 ml ofmethanol. A white solid product was precipitated, recovered byfiltration, and then dried to obtain 0.45 g of a solid product.

The polymerization activity of 1.9 Kg/gTi.

Comparative Example 7

In a 100 ml flask, 25 mmol of norbornadiene, 0.005 mmol of(cyclopentadienyl)trimethyltitanium and 0.005 mmol of aluminoxane werereacted in 50 ml of toluene at 20° C. for 4 hours, but a polymer was notobtained.

Example 75

(1) Preparation of Triethylammonium

Tetrakis(pentafluorophenyl)borate:

In the same manner as in Example 1, 12.8 mol of triethylammoniumtetrakis(pentafluorophenyl)borate was prepared, and dissolved in 1280 mlof toluene to obtain a catalyst solution.

(2) Preparation of Dimethylsilylenebis(cyclopentadienyl)dichlorozirconium:

Dicyclopentadienyldimethylsilane (1.73 g; 9.19 mmol) was dissolved in 50ml of dehydrated tetrahydrofuran. To the obtained solution, 12.0 ml(18.6 mmol) of a butyllithium/hexane solution (1.55 mol/1) was addeddropwise at -75° C. over a period of 1 hour. After agitation for 30minutes, the reaction mixture was heated to 0° C. To the obtainedreaction mixture, 50 ml of dehydrated tetrahydrofuran containing 2.14 g(9.18 mmol) of zirconium tetrachloride dissolved therein, was addeddropwise over a period of 1 hour. Then, the reaction mixture was stirredat room temperature over night. After the reaction mixture was heated to50° C. for 2 hours, the solvent was removed to obtain a solid product.The obtained solid, product was washed with a small amount of cooledpentane. Further, the solid product was subjected to a methylenechloride extraction and recrystallization by concentration to obtain2.20 g (6.31 mmol) of dimethylsilylenebiscyclopentadienyl)dichlorozirconium (Reference: Inorg., Chem., Vol. 24,Page 2539 (1985)).

The obtained product was suspended in 631 ml of toluene to obtain acatalyst solution.

(3) Copolymerization of Norbornene and Ethylene:

A 500 ml glass autoclave purged with nitrogen, was charged with 200 mlof toluene and 1.0 mmol of triisobutylaluminum. Further, 10 micromol ofdimethylsilylenebis,(cyclopentadienyl)dichlorozirconium obtained in Step(2) above and 10 micromol of triethylammoniumtetrakis(pentafluorophenyl)borate obtained in Step (1) above were addedto the reaction mixture. Then, 22 mmol of norbornene was added. Afterthe reaction mixture was heated to 50° C., the polymerization wascarried out at normal pressure for 1 hour while introducing ethylene gasat a rate of 40 l/hr. The polymerization was proceeded in a uniformsolution state. After completion of the reaction, the reaction solutionwas placed into 1 liter of HCl acidic methanol to precipitate a polymer.After, the catalyst components were removed by decomposition, theproduct was washed and dried to obtain 1.47 g of a copolymer. Thepolymerization activity was 1.6 Kg/gZr.

The obtained copolymer had a norbornene content of 68 mol %; anintrinsic viscosity of 0.3 dl/g; a glass transition temperature (Tg) of182° C.; and a softening point (TMA) of 1750° C. A sheet made of thecopolymer had an all light transmittance of 94.0% and haze of 3.2%.

Example 76

The procedures of Example 75 were repeated except that the amount ofnorbornene used was changed to 44 mmol in Step (3). As a result, 1.64 gof a copolymer were obtained. The polymerization activity was 1.8Kg/gZr.

The obtained copolymer had a norbornene content of 74 mol %; anintrinsic viscosity of 0.49 dl/g; a glass transition temperature (Tg) of199° C.; and a softening point (TMA) of 190° C. A sheet made of thecopolymer had an all light transmittance of 94.5% and haze of 3.0%.

Example 77

The procedures of Example 75 were repeated except that the amount ofnorbornene used was changed to 33 mmol in Step (3). As a result, 2.44 gof a copolymer were obtained. The polymerization activity was 2.7Kg/gZr.

The obtained copolymer had a norbornene content of 72 mol %; anintrinsic viscosity of 0.50 dl/g; a glass transition temperature (Tg) of193° C.; a softening point (TMA) of 185° C.; a tensile strength of 260Kg/cm² ; an elongation of 1%; and a tensile modulus of 29,000 Kg/cm². Asheet made of the copolymer had an all light transmittance of 93% andhaze of 3%.

Example 78

The procedures of Example 75 were repeated except that 10 micromol ofbis(cyclopentadienyl)dichlorozirconium was used instead ofdimethylsilylenebis (cyclopentadienyl)dichlorozirconium in Step (3). Asa result, 1.86 g of a copolymer were obtained. The polymerizationactivity was 2.0 Kg/gZr.

The obtained copolymer had a norbornene content of 4 mol %; and anintrinsic viscosity of 0.76 dl/g. The glass transition temperature (Tg)could not be measured at room temperature or higher.

Example 79

(1) Preparation of Dimethylsilylenebis(indenyl)dichlorozirconium:

The procedures of Step (2) of Example 75 were repeated to prepare 0.61 g(1.36 mmol) of dimethylsilylenebis(indenyl)dichlorozirconium, exceptthat 2.65 g (9.2 mmol) of diindenyldimethylsilane was used instead ofdicyclopentadienyldimethylsilane (Reference: Angew. Chem. Int. Ed.Engl., Vol. 28, Page 1511 (1989)).

The obtained product was suspended in 136 ml of toluene to prepare acatalyst solution.

(2) Copolymerization of Norbornene/Ethylene:

The procedures of Step (3) of Example 75 were repeated except that 10micromol of dimethylsilylenebis(indenyl)dichlorozirconium was usedinstead of dimethylsilylenebis(cyclopentadienyl)dichlorozirconium, andthe amount of norbornene used was changed to 66 mmol. As a result, 3.38g of a copolymer were obtained. The polymerization activity was 3.7Kg/gZr.

The obtained copolymer had a norbornene content of 67 mol %; anintrinsic viscosity of 1.4 dl/g; a glass transition temperature (Tg) of176° C.; and a softening point (TMA) of 168° C. A sheet made of thecopolymer had an all light transmittance of 94.0% and haze of 3.1%.

Example 80

The procedures of Step (2) of Example 79 were repeated except that theamount of norbornene used was changed to 100 mmol. As a result, 2.88 gof a copolymer were obtained. The polymerization activity was 3.2Kg/gZr.

The obtained copolymer had a norbornene content of 72 mol %; anintrinsic viscosity of 1.2 dl/g; a glass transition temperature (Tg) of205° C.; and a softening point (TMA) of 195° C.

Comparative Example 8

The procedures of Step (3) of Example 75 were repeated except that 1.0ml (1.0 mmol) of a toluene solution (1 mol/l ) containingethylaluminumsesquichloride (Al(C₂ H₅)₁.5 Cl₁.5) was used instead oftriisobutylaluminum; 0.25 ml (0.25 mmol) of a toluene solution (1 mol/l) containing VO(OC₂ H₅)Cl₂ was used instead ofdimethylsilylenebis(cyclopentadienyl)dichlorozirconium; triethylammoniumtetrakis(pentafluorophenyl)borate was not used; and the amount ofnorbornene used was changed to 100 mmol. As a result, 1.38 g of acopolymer were obtained. The polymerization activity was 0.11 Kg/gZr.

The obtained copolymer had a norbornene content of 48 mol %; anintrinsic viscosity of 1.2 dl/g; a glass transition temperature (Tg) of104° C.; and a softening temperature (TMA) of 98° C.

Example 81

(1) Synthesis of Catalyst Component (B):

The procedures of Example 15 were repeated to prepare ferroceniumtetrakis(pentafluorophenyl)borate.

(2) Polymerization:

A 30 liter autoclave was charged with 8 liter of dried toluene, 12 ml oftriisobutylaluminum, 0.6 mmol of ferroceniumtetrakis(pentafluorophenyl)borate as obtained in Step (1), 0.6 mmol ofbis(cyclopentadienyl)dimethylzirconium and 4 mol of norbornene. Thepolymerization was carried out at 50° C., at an ethylene pressure of 5Kg/cm².G for 1 hour. After completion of the reaction, the polymersolution was placed in 15 liter of methanol to precipitate a polymer.The polymer was recovered by filtration to obtain 2.4 Kg of a copolymer.The polymerization conditions are as shown in Table 1. Thepolymerization activity was 44 Kg/gZr.

The obtained copolymer had a norbornene content of 6 mol %; an intrinsicviscosity of 2.10 dl/g; and a crystalline degree of 16%.

It was found that the polymer obtained had a random structure since ithad low crystallization degree and good transparency.

(3) Molding of Sheet:

The copolymer obtained in Step (2) above was subjected to T-die moldingusing 20 mm extruder with a lip gap of 0.5 mm at a screw rotation rateof 30 rpm at a lip temperature of 205° C., to prepare a sheet having athickness of 0.2 mm. The results of measurement of optical properties,and physical properties such as modulus, an elastic recovery propertyare as shown in Table 2.

Examples 82 to 86

The similar procedures of Example 81 were repeated to prepare severalcopolymers with different norbornene content and 0.2 mm thick sheetstherefrom. The polymerization conditions are as shown in Table 1. Theresults of evaluation of the sheets obtained in physical properties areas shown in Table 2.

It was found that these copolymer obtained had a random structure sinceit had low crystallization degree and good transparency.

Example 87

Under the conditions as shown in Table 1, an ethylene/norbornenecopolymer having an intrinsic viscosity of 1.69 dl/g and a norbornenecontent of 23.7 mol % was synthesized. The 0.2 mm thick sheet obtainedfrom the copolymer was evaluated in an elastic recovery property. As aresult, the sheet was torn before 150% elongation and the elasticrecovery property could not be measured. The results of the physicalproperty testing of the sheet obtained are as shown in Table 2.

Comparative Example 9

A 0.2 mm thick sheet was prepared from conventional high densitypolyethylene (IDEMITSU 640UF: Manufactured by Idemitsu Petrochemical).The sheet obtained showed an elastic recovery of -50%. The results ofthe physical property measurement of the sheet obtained are as shown inTable 2.

Comparative Example 10

A 0.2 mm thick sheet was prepared from a conventionalethylene/alpha-olefin copolymer (MOATEC 0168N: Manufactured by IdemitsuPetrochemical). The sheet obtained showed an elastic recovery of -15%.The results of the physical property measurement of the sheet obtainedare as shown in Table 2.

                                      TABLE 1                                     __________________________________________________________________________                                       *.sup.4                                    Catalyst Component          Amount of                                                                            Ethylene                                                                           Polymerization                                                                        Yield                                                                             Activity                        (A) *.sup.1                                                                          (B) *.sup.2                                                                          (C) *.sup.3                                                                           Norbornene                                                                           Pressure                                                                           Temperature                                                                           kg  kg/gZr                    __________________________________________________________________________    Example 81                                                                          ZM 0.6 mmol                                                                          F 0.6 mmol                                                                           TIBA 12 mmol                                                                          4 mmol 5    50° C.                                                                         2.4 44                        Example 82                                                                          ZC 0.4 mmol                                                                          F 0.4 mmol                                                                           TIBA  8 mmol                                                                          4 mmol 10   50° C.                                                                         0.7 19                        Example 83                                                                          ZM 0.6 mmol                                                                          AN 0.6 mmol                                                                          TIBA 12 mmol                                                                          4 mmol 5    50° C.                                                                         1.8 33                        Example 84                                                                          ZC 0.6 mmol                                                                          AN 0.6 mmol                                                                          TIBA 12 mmol                                                                          8 mmol 5    50° C.                                                                         0.8 15                        Example 85                                                                          ZC 0.4 mmol                                                                          AN 0.4 mmol                                                                          TIBA  8 mmol                                                                          6 mmol 5    50° C.                                                                         0.5 14                        Example 86                                                                          ZC 0.6 mmol                                                                          AN 0.6 mmol                                                                          TIBA 12 mmol                                                                          5 mmol 5    50° C.                                                                         2.0 37                        Example 87                                                                          ZC 1.0 mmol                                                                          AN 1.0 mmol                                                                          TIBA 20 mmol                                                                          4 mmol 3    50° C.                                                                         0.8 9                         __________________________________________________________________________     *.sup.1 : ZM . . . bis (cyclopentadienyl) dimethyl zirconium ZC . . . bis     (cyclopentadienyl) dichlorozirconium                                          *.sup.2 : F . . . ferrocenium tetra (pentafluorophenyl) borate AN . . .       dimethylanilinium tetra (pentafluorophenyl) borate                            *.sup.3 : TIBA . . . triisobutylaluminum                                      *.sup.4 : Unit is Kg/cm.sup.2 G                                          

                                      TABLE 2                                     __________________________________________________________________________           Copolymers                                                                                        Molecular                                                                            Sheet                                                  NB   Crystallization                                                                          Weight Tensile                                                                            Elastic                                                                             All Light                               [η]                                                                           Content                                                                            Degree  Tg Distribution                                                                         Modulus                                                                            Recovery                                                                            Transmittance                           (dl/g)                                                                            (mol %)                                                                            (%)     (°C.)                                                                     Mw/Mn  (Kg/cm.sup.2)                                                                      (%)   (%)                              __________________________________________________________________________    Example 81                                                                           2.10                                                                              6.0  16      0  1.71   561  70    95                               Example 82                                                                           3.61                                                                              4.3  26      -7 1.99   881  35    94                               Example 83                                                                           2.71                                                                              8.5  13      4  1.85   452  66    95                               Example 84                                                                           1.00                                                                              16.4 1 or lower                                                                            14 1.64   365  81    95                               Example 85                                                                           1.23                                                                              12.5 1 or lower                                                                            11 1.73   300  94    95                               Example 86                                                                           2.19                                                                              8.8  11      5  1.78   355  78    95                               Example 87                                                                           1.69                                                                              23.7 --      42 1.95   28,900                                                                             Break 95                               Comp. Ex. 9                                                                          3.13                                                                              0    --      -- --     10,900                                                                             -50   93                               Comp. Ex. 10                                                                         1.96                                                                              0    --      -- --     7,400                                                                              -15   95                               __________________________________________________________________________

Example 88

(1) Preparation of Dimethylanilinium

Tetrakis(pentafluorophenyl)borate:

Pentafluorophenyllithium prepared from 152 mmol ofbromopentafluorobenzene and 152 mmol of butyllithium was reacted with 45mmol of boron trichloride in hexane, to obtaintri(pentafluorophenyl)boron as a white solid product.

The obtained tris(pentafluorophenyl)boron (41 mmol) was reacted with anether solution of pentafluorophenyllithium (41 mmol) in hexane, toisolate lithium tetrakis(pentafluorophenyl)borate as a white solidproduct.

Thereafter, lithium tetrakis(pentafluorophenyl)borate (16 mmol) wasreacted with dimethylaniline hydrochloride (16 mmol) in water, to obtain11.4 mmol of dimethylanilinium tetrakis(pentafluorophenyl)borate as awhite solid product.

It was confirmed by ¹ H-NMR and ¹³ C-NMR that the reaction product wasthe target product.

(2) Copolymerization of Norbornene/Ethylene

In a 1 liter autoclave, under nitrogen atmosphere at room temperature,400 ml of toluene, 0.6 mmol of triisobutylaluminum (TIBA), 3 micromol ofbis(cyclopentadienyl)dichlorozirconium, and 4 micromol ofdimethylanilinium tetrakis(pentafluorophenyl)borate obtained in Step (1)above were charged in this order. Then, 400 mmol of norbornene wasadded. After the reaction mixture was heated to 90° C., thepolymerization was carried out for 90 minutes while introducing ethylenegas so as to keep the ethylene partial pressure to 7 Kg/cm².

After completion of the reaction, the polymer solution was placed into 1liter of methanol to precipitate a polymer. The polymer was recovered byfiltration, and dried.

The catalyst components, polymerization conditions and yield of thecopolymer in this Example are as shown in Table 3. Further, thenorbornene content, intrinsic viscosity, crystallization degree, glasstransition temperature (Tg), weight average molecular weight (Mw),number average molecular weight (Mn), molecular weight distribution(Mw/Mn) and melting point (Tm) of the copolymer obtained, are as shownin Table 4.

In the copolymer obtained in Example 88, a broad melt peak was sheen at75° C. The DSC chart is as shown in FIG. 2.

(3) Molding of Sheet:

The copolymer obtained in Step (2) above was subjected to heat pressmolding at 190° C. and at a pressure of 100 Kg/cm², to obtain a 0.1 mmthick sheet.

The tensile modulus, tensile breaking strength, tensile breakingelongation, elastic recovery, all light transmittance and haze weremeasured, and are as shown in Table 4.

Comparative Example 11

(1) Copolymerization of Norbornene and Ethylene:

A 1 liter autoclave, under nitrogen atmosphere, was charged with 400 mlof toluene, 8 mmol of ethylaluminum sesquichloride (Al(C₂ H₅)₁.5 Cl₁.5),0.8 mmol of VO(OC₂ H₅)Cl₂ and 130 mmol of norbornene. After the reactionmixture was heated to 40° C., the polymerization was carried out for 180minutes while continuously introducing ethylene so as to keep theethylene partial pressure to 3 Kg/cm².

After completion of the reaction, the polymer solution was placed into 1liter of methanol to precipitate a polymer. The polymer was recovered byfiltration, and dried.

(2) Molding of Sheet:

The procedures of Step (3) of Example 88 were repeated using thecopolymer obtained in Step (1) above. The results are as shown in Table4. In the DSC measurement of the copolymer obtained in ComparativeExample 11, a sharp melt peak was recognized at 100° C. The DSC chart isas shown in FIG. 3.

Example 89

(1) Copolymerization of Ethylene and Norbornene:

The procedures of Step (2) of Example 88 were repeated except thatferrocenium tetrakis(pentafluorophenyl)borate was used instead ofdimethylanilinium tetrakis(pentafluorophenyl)borate, and the otherconditions were changed as indicated in Table 3.

(2) Molding of Sheet:

The procedures of Step (3) of Example 88 were repeated using thecopolymer obtained in Step (1) above. The results are as shown in Table4.

Examples 90 to 94

(1) Preparation of Catalyst and

(2) Copolymerization of Ethylene and Norbornene:

The procedures of Example 88 were repeated except that catalystcomponents and polymerization conditions were changed as indicated inTable 3, to obtain copolymers. FIG. 4 shows a ¹³ C-NMR char of thecopolymer obtained in Example 91.

(2) Molding of Sheet:

The procedures of Step (3) of Example 88 were repeated using thecopolymers obtained in Step (2) above. The results are as shown in Table4.

                                      TABLE 3                                     __________________________________________________________________________                          Amount                                                         Catalyst Components                                                                          of     Ethylene                                                                           Polymerization                                                                        Polymerization                                                                        Yield of                           (A) *.sup.1                                                                       (B) *.sup.2                                                                       (C)    Norbornene                                                                           Pressure                                                                           Temperature                                                                           Time    Copolymer                          (μmol)                                                                         (μmol)                                                                         TIBA (mmol)                                                                          (mmol) (Kg/cm.sup.2)                                                                      (°C.)    (g)                         __________________________________________________________________________    Example 88                                                                           ZC 3                                                                              AN 4                                                                              0.6    400    7    90      90      85.6                        Example 89                                                                           ZC 10                                                                             F 10                                                                              0.6    200    10   50      60      37.3                        Example 90                                                                           ZM 15                                                                             AN 15                                                                             0.6    200    5    50      60      41.6                        Example 91                                                                           ZC 25                                                                             AN 25                                                                             0.6    200    3    50      30      8.9                         Example 92                                                                           ZC 20                                                                             AN 20                                                                             0.6    200    3    50      60      15.3                        Example 93                                                                           ZC 15                                                                             AN 15                                                                             0.6    200    5    50      30      10.4                        Comp. Ex. 11                                                                         130 3   40     180    14.6                                             Example 94                                                                           ZC 25                                                                             AN 25                                                                             0.6    200    2    50      30      8.3                         __________________________________________________________________________     *.sup.1 : ZM . . . bis (cyclopentadienyl) dimethyl zirconium ZC . . . bis     (cyclopentadienyl) dichlorozirconium                                          *.sup.2 : F . . . ferroceniumtetra (pentafluorophenyl) borate AN . . .        dimethylanilinium tetra (pentafluorophenyl) borate                       

                                      TABLE 4                                     __________________________________________________________________________    Copolymers                           Sheets                                                Crys-          Molecular                                                                              Tensile  Elon-                           Nor-         talliza-       Weight   Modu-                                                                             Tensile                                                                            gation                                                                            Elastic                                                                            All Light              bornene   [η]                                                                          tion           Distri-  lus Strength                                                                           at  Re-  Transmit-              Content   (dl/                                                                             Degree                                                                            Tg         bution                                                                              Tm (Kg/                                                                              at Break                                                                           Break                                                                             covery                                                                             tance                                                                              Haze              (mol %)   g) (%) (°C.)                                                                     Mw  Mn  Mw/Mn (°C.)                                                                     cm.sup.2)                                                                         (Kg/cm.sup.2)                                                                      (%) (%)  (%)  (%)               __________________________________________________________________________    Example                                                                            8.5  1.56                                                                             1.5 3  86900                                                                             45300                                                                             1.91  75 329 354  441 84   94   3.3               88                                                                            Example                                                                            4.3  3.61                                                                             26  -7 210000                                                                            105000                                                                            2.00  86 881 452  468 35   94   3.7               89                                                                            Example                                                                            8.5  2.71                                                                             13  4  137000                                                                            73800                                                                             1.85  77 452 431  453 66   95   3.0               90                                                                            Example                                                                            16.4 1.00                                                                             0.8 14 57500                                                                             35000                                                                             1.64  26 365 358  448 93   95   2.8               91                                                                            Example                                                                            12.5 1.23                                                                             0.9 11 72600                                                                             42100                                                                             1.73  31 300 276  411 94   95   2.7               92                                                                            Example                                                                            8.8  2.19                                                                             11  5  29000                                                                             72700                                                                             1.78  69 355 376  418 78   95   3.0               93                                                                            Comp.                                                                              9.4  1.18                                                                             2.0 1  348000                                                                            109000                                                                            3.20  100                                                                              3800                                                                              289  290  5   90   12.3              Ex. 11                                                                        Example                                                                            24.6 1.21                                                                             0   50 357000                                                                            83900                                                                             4.26  -- 23900                                                                             490  2.3 Unable                                                                             93   3.0               94                                                to                                                                            Measure                     __________________________________________________________________________

Example 95

(1) Preparation of Ferrocenium

Tetrakis(pentafluorophenyl)borate:

Ferrocenium tetrakis(pentafluorophenyl)borate was prepared in the samemanner as in Example 15.

(2) Copolymerization of Norbornene and Ethylene:

In a 30 liter autoclave, in a nitrogen atmosphere at room temperature,15 liter of toluene, 23 mmol of triisobutylaluminum (TIBA), 0.11 mmol ofbis(cyclopentadienyl)dichlorozirconium, and 0.15 mmol of ferroceniumtetrakis(pentafluorophenyl)borate obtained in Step (1) above, werecharged in this order. Then, 2.25 liters of a 70 wt. % toluene solutioncontaining 15.0 mol of norbornene was added to the reaction mixture.After the reaction mixture was heated to 90° C., the polymerization wascarried out for 110 minutes while continuously introducing ethylene soas to keep the ethylene partial pressure to 7 Kg/cm².

After completion of the reaction, the polymer solution was placed into15 liters of methanol to precipitate a polymer. The polymer wasrecovered by filtration, and dried, to obtain a cyclic olefin basedcopolymer (a1).

The yield of the cyclic olefin based copolymer (a1) was 3.48 Kg. Thepolymerization activity was 347 Kg/gZr.

The obtained cyclic olefin based copolymer (a1) had a norbornene contentof 9.2 mol %; an intrinsic viscosity of 0.99 dl/g; a crystallizationdegree of 1.0%; a glass transition temperature (Tg) of 3° C.; a weightaverage molecular weight (Mw) of 54,200; a number average molecularweight (Mn) of 28,500; a molecular weight distribution of 1.91; and amelting point of 73° C. (broad peak).

Example 96

To 100 parts by weight of a pulverized product of the cyclic olefincopolymer (a1) obtained in Example 95, 1.05 parts by weight ofdiatomaceous earth as anti-blocking agent, 0.25 parts by weight ofelucic acid amide as lubricant, 10.7 parts by weight of L-LDPE asalpha-olefin based polymer (0438N: Manufactured by IdemitsuPetrochemical; MI=4 g/10 min.; D=0.920 g/cm3), were added and mixed. Themixture was supplied to a 50 mm .O slashed.uniaxial extruder. Themixture was extruded by a circular die with a diameter of 100 mm and agap of 3 mm at 160° C., and then subjected to inflation molding toobtain a film having a thickness of 20 micrometers and a width of afolded portion of 340 mm. The extruding rate was 7 Kg/hr and the pullingrate was 6.0 m/min. The moldability was excellent.

The physical properties such as tensile properties and elastic recoveryproperty, and optical properties of the film obtained were measured, andare as shown in Table 5.

In addition, the measurement methods were completely the same throughthe following Examples.

Example 97

The procedures of Example 95 were repeated except that in Step (2) ofExample 95, the amount of bis(cyclopentadienyl)dichlorozirconium usedwas changed to 0.075 mmol and the amount of norbornene used was changedto 7.5 mol, to obtain a cyclic olefin copolymer (a2).

The yield of the cyclic olefin copolymer (a2) was 2.93 Kg. Thepolymerization activity was 428 Kg/gZr.

The obtained cyclic olefin copolymer (a2) had a norbornene content of4.9 mol %; an intrinsic viscosity of 1.22 dl/g; a glass transitiontemperature (Tg) of -7° C.; a weight average molecular weight (Mw) of72,400; a number average molecular weight (Mn) of 36,400; a molecularweight distribution of 1.99; and a melting point (Tm) of 84° C. (broadpeak).

Examples 98 to 104

The procedures of Example 96 were repeated except that the kind ofcomponents and the amount of the components used were changed asindicated in Table 5. The results of the physical property measurementare also as shown in Table 5.

Example 105

The copolymer obtained in Step (2) of Example 95 were subjected to heatpressing at 190° C. at a pressure of 100 Kg/cm², to obtain a sheethaving a thickness of 0.1 mm. The results of the physical propertymeasurement were as shown in Table 5.

                                      TABLE 5                                     __________________________________________________________________________    Norbornene  Compo-                                                                             Compo-    Component      Tensil                                                                             Elon-                                                                              Elastic                                                                              Heat               Based       nent nent [b]                                                                           Compo-                                                                             [c]   Mold-                                                                             Tensil                                                                             Strength                                                                           gation                                                                             Recov- Seal               Copolymer   [b]  Weight                                                                             nent Weight                                                                              abil-                                                                             Molulus                                                                            at Break                                                                           at Break                                                                           ery Haze                                                                             Temp.              Kind        kind (pbw)                                                                              [c]  (pbw) ity (Kg/cm.sup.2)                                                                      (Kg/cm.sup.2)                                                                      (%)  (%) (%)                                                                              (°C.)       __________________________________________________________________________    Example                                                                            a1     *1   1.05 L-LDPE                                                                             10.7  good                                                                              510  450  640  83  9.4                                                                              82                 96          *2   0.25                                                         Example                                                                            a1     *1   1.05 --   --    good                                                                              480  460  690  87  4.9                                                                              78                 98          *2   0.25                                                         Example                                                                            a1     *1   0.50 L-LDPE                                                                             5.0   good                                                                              500  450  650  85  7.6                                                                              81                 99          *2   0.10                                                         Example                                                                            a1     *1   0.50 L-LDPE                                                                             5.0   good                                                                              470  450  620  80  7.2                                                                              83                 100         *3   0.10                                                         Example                                                                            a1     *1   0.50 --   --    good                                                                              450  430  650  87  4.0                                                                              79                 101         *3   0.10                                                         Example                                                                            a2     *4   0.50 L-LDPE                                                                             5.0   good                                                                              880  452  470  59  9.7                                                                              91                 102         *2   0.10                                                         Example                                                                            a2     *4   0.50 --   --    good                                                                              820  470  490  62  4.5                                                                              89                 103         *2   0.10                                                         Example                                                                            a1     --   --   --   --    poor                                                                              Inflation films could not be stably                                           prepared.                                104                                                                           Example                                                                            a1                              561  560  602  70  3.0                                                                              78                 105                                                                           __________________________________________________________________________     *1: Diatomaceous earth                                                        *2: Erucic acid amide                                                         *3: Stearic acid                                                              *4: Silica                                                               

Example 106

To 100 parts by weight of a pulverized product of the cyclic olefincopolymer (a1) obtained in Example 95, 0.2 parts by weight ofdiatomaceous earth as anti-blocking agent, and 0.05 parts by weight ofelucic acid amide as lubricant, were added and mixed. The mixture wassupplied to a 50 mm .O slashed.uniaxial extruder. The mixture wasextruded by a circular die with a diameter of 100 mm and a gap of 3 mmat 160° C., and then subjected to inflation molding to obtain a wrappingfilm having a thickness of 15 micrometers and a width of a foldedportion of 450 mm. The extruding rate was 7 Kg/hr and the pulling ratewas 12 m/min. The moldability was excellent.

The physical properties such as tensile properties, elastic recoveryproperty and gas permeability, and optical properties of the filmobtained were measured, and are as shown in Table 6 or 7.

Examples 107 to 110 and Comparative Examples 12 to 14

The procedures of Example 106 were repeated except that the kind ofcomponents and the amount of the components used were changed asindicated in Table 6. The results of the physical property measurementare as shown in Table 6 or 7.

                                      TABLE 6                                     __________________________________________________________________________    Cyclic Ole-                                                                             Mold-                                                                             Film         *4   Tensil *4                                                                          *4       Elastic                                                                           Heat                                                                              Self                    fin Based ing Thick-                                                                            Mold-                                                                             Tensile                                                                            Tensile                                                                            Strength                                                                           Elongation                                                                             Recov-                                                                            Seal                                                                              Ad- Stabbing            Copolymer Temp.                                                                             ness                                                                              abil-                                                                             Strength                                                                           Modulus                                                                            at Break                                                                           at Break                                                                            Haze                                                                             ery Temp.                                                                             hesive-                                                                           Strength            Kind      (°C.)                                                                      (μ)                                                                            ity (Kg/cm)                                                                            (Kg/cm.sup.2)                                                                      (Kg/cm.sup.2)                                                                      (%)   (%)                                                                              (%) (°C.)                                                                      ness                                                                              (g)                 __________________________________________________________________________    Exam-                                                                             a1    160 15  good                                                                              199  480  460  690   1.5                                                                              87  78  ∘                                                                     240                 ple 106                    (206)                                                                              (718)                                                                              (196)                                    Exam-                                                                             a1    160 40  good                                                                              205  503  490  710   2.3                                                                              83  80  ∘                                                                     600                 ple 107                    (220)                                                                              (774)                                                                              (191)                                    Exam-                                                                             a1    180 15  good                                                                              191  489  475  650   1.4                                                                              85  78  ∘                                                                     250                 ple 108                    (210)                                                                              (721)                                                                              (204)                                    Exam-                                                                             a2    160 15  good                                                                              394  721  518  580   1.3                                                                              70  84  ∘                                                                     310                 ple 109                    (339)                                                                              (818)                                                                              (154)                                    Exam-                                                                             a2    160 40  good                                                                              408  742  538  555   1.6                                                                              66  86  ∘                                                                     825                 ple 110                    (358)                                                                              (859)                                                                              (155)                                    Comp.                                                                             *1    --  14  --   78  880  330  96    1.6                                                                              broken                                                                            --  ∘                                                                      96                 Ex. 12                                                                            PVC                    (18600)                                                                            (661)                                                                              (33)                                     Comp.                                                                             (MD) *2                                                                             --  14  --  (TD) 2000 660  51    1.3                                                                              broken                                                                            --  ∘                                                                     149                 Ex. 13                                                                            poly-             (MD) (35400)                                                                            (1477)                                                                             (23)                                         butadiene         not 4.4                                                                       broken                                                  Comp.                                                                             *3    160 30  good                                                                              100  1400 400  500   4.6                                                                              -15 97  x   170                 Ex. 14                                                                            LLDPE                  (12400)                                                                            (433)                                                                              (194)                                    __________________________________________________________________________     *1 Commerial Product                                                          *2 Commerial Product                                                          *3 V0398CN (manufactured by Idemitsu Petrochemical)                           *4 Results measured at room temperature (-40° C.) are shown.      

                                      TABLE 7                                     __________________________________________________________________________            Oxygen    Nitrogen  Moisture                                                  Permeability                                                                            Permeability                                                                            Permeability                                              (ml/m.sup.2 · 24 h · atm)                                             (ml/m.sup.2 · 24 h · atm)                                             (g/m.sup.2 · 24 h ·             __________________________________________________________________________                                atm)                                              Example 106                                                                           8600      1700      28                                                Example 107                                                                           3200      650       14                                                Example 108                                                                           8700      1600      29                                                Example 109                                                                           8600      1500      30                                                Example 110                                                                           3400      800       13                                                Comp. Ex. 12                                                                          1700      460       68                                                Comp. Ex. 14                                                                          13200     3300      26                                                __________________________________________________________________________

Example 111

The procedures of Example 95 were repeated except that in Step (2) ofExample 95, the amount of bis(cyclopentadienyl)dichlorozirconium usedwas changed to 0.064 mmol; the amount of ferroceniumtetrakis(pentafluorophenyl)borate used was changed to 0.11 mmol; theamount of norbornene used was changed to 7.5 mol; the polymerizationtemperature was changed to 70° C.; and the ethylene partial pressure waschanged to 9 Kg/cm², to obtain a cyclic olefin copolymer (a3).

The yield of the cyclic olefin copolymer (a3) was 2.36 Kg. Thepolymerization activity was 404 Kg/gZr.

The obtained cyclic olefin copolymer (a3) had a norbornene content of4.5 mol %; an intrinsic viscosity of 3.07 dl/g; a glass transitiontemperature (Tg) of -8° C.; a weight average molecular weight (Mw) of213,000; a number average molecular weight (Mn) of 114,000; a molecularweight distribution of 1.87; and a melting point (Tm) of 81° C. (broadpeak).

Comparative Example 15

The procedures of Example 95 were repeated except that in Step (2) ofExample 95, 300 mmol of ethylaluminumsesquichloride was used instead oftriisobutylaluminum; 30 mmol of VO(OC₂ H₅)Cl₂ was used instead ofbis(cyclopentadienyl)dichlorozirconium; ferroceniumtetrakis(pentafluorophenyl)borate was not used; the amount of norborneneused was changed to 3 mol; the polymerization temperature was changed to30° C.; the ethylene partial pressure was changed to 1 Kg/cm² ; and thepolymerization time was changed to 30 minutes, to obtain a cyclic olefincopolymer (a4).

The yield of the cyclic olefin copolymer (a4) was 480 g.

The obtained cyclic olefin copolymer (a4) had a norbornene content of24.6 mol %; an intrinsic viscosity of 1.21 dl/g; a glass transitiontemperature (Tg) of 50° C.; a molecular weight distribution of 4.26; anda melting point+(Tm) of 100° C. (sharp peak).

Examples 112 to 116 and Comparative Examples 16 and 17

As indicated in Table 8, pellets prepared from the cyclic olefincopolymers (a1) to (a4) obtained in Examples 95, 97 and 111 andComparative Example 15, or resin compositions containing the copolymer(a1), (a2), (a3) or (a4) and a thermoplastic resin, were subjected toinjection molding using an injection molding equipment (IS25EP:Manufactured by Toshiba) at a setting temperature of 150° C., at a moldtemperature of 30° C., an injection pressure (first/second) of 80/40Kg/cm², to obtain a molded article (70 mm×70 mm×2 mm).

The physical properties such as tensile properties and molding shrinkagefactor, and optical properties of the molded articles obtained, weremeasured, and are as shown in Table 8.

                                      TABLE 8                                     __________________________________________________________________________                                             Mold-                                                                             Mold-                                                                     ing ing                                                         Elon-                                                                             Izod Izod Un-                                                                           Shrink-                                                                           Shrink-                                                                           Ol-    All                   Cyclic                 Tensile                                                                           ga- Notched                                                                            notched                                                                            age age zen    Light                 Olefin  Ther- A-  tensile                                                                            Modu-                                                                             tion                                                                              Impact                                                                             Impact                                                                             Factor                                                                            Factor                                                                            Stif-                                                                            Shore                                                                             Trans-                Based   mo-   mount                                                                             Strength                                                                           lus tion at                                                                           Strength                                                                           Strength                                                                           (length                                                                           (width                                                                            ness                                                                             Hard-                                                                             mit-                  Copol-  plastic                                                                             Used                                                                              at Break                                                                           (Kg/                                                                              Break                                                                             (Kgcm/                                                                             (Kgcm/                                                                             direc-                                                                            direc-                                                                            (Kg/                                                                             ness                                                                              tance                                                                             Haze              ymer    Resim (pbw)                                                                             (Kg/cm.sup.2)                                                                      cm.sup.2)                                                                         (%) cm)  cm)  tion)                                                                             tion)                                                                             cm.sup.2)                                                                        (D) (%) (%)               __________________________________________________________________________    Exam-                                                                             a1  --    --  360  490 440 NB*.sup.4                                                                          NB   0.35                                                                              1.33                                                                              205                                                                              46  92.2                                                                              4.5               ple 112                                                                       Exam-                                                                             a2  --    --  420  760 530 NB   NB   0.27                                                                              0.77                                                                              220                                                                              48  93.8                                                                              4.2               ple 113                                                                       Exam-                                                                             a3  --    --  440  840 510 NB   NB   0.47                                                                              0.98                                                                              235                                                                              51  91.0                                                                              5.3               ple 114                                                                       Exam-                                                                             a1  L.LDPE*.sup.1                                                                       10  380  540 430 NB   NB   0.91                                                                              1.25                                                                              260                                                                              55  90.7                                                                              11                ple 115                                                                       Exam-                                                                             a1  IPP*.sup.2                                                                          10  390  580 400 NB   NB   1.32                                                                              1.48                                                                              280                                                                              59  89.3                                                                              14                ple 116                                                                       Comp.                                                                             --  TPO*.sup.3                                                                          --  310  3300                                                                              870 NB   NB   1.41                                                                              1.28                                                                              195                                                                              62  28.1                                                                              90                Ex. 16                                                                        Comp.                                                                             a4  --    --  580  25000                                                                              6  8    70   0.5 0.7 2500                                                                             99  86.6                                                                              15                Ex.17                                                                         __________________________________________________________________________     *.sup.1 Linear low density polyethylene (V0398CN manufactured by Idemitsu     Petrochemical)                                                                *.sup.2 Polypropylene (Manufactured by Idemitsu Petrochemical)                *.sup.3 Olefin based thermoplastic elastomer (SP × 9800 Manufactred     by Mitsubishi Yuka)                                                           *.sup.4 Not Broken                                                       

Example 117

A 500 ml glass vessel was charged with 30 ml of dried toluene, 5 mmol oftriisobutylaluminum, 25 micromoles of nickel bis(acetylacetonate), 25micromoles of dimethylanilinium tetrakis(pentafluorophenyl)borate and500 mmol of norbornene. The polymerization was carried out at 50° C. for1 hour, to obtain 9.58 g of a polymer. The polymerization activity was6.53 Kg/gNi.

The obtained copolymer had a weight average molecular weight (Mw) of1,210,000 and a molecular weight distribution of 2.37.

Reference Example 1

The procedures of Example 13 were repeated except that 2.0 mmol ofmethylaluminoxane was employed instead of triisobutylaluminum, andtriethylammonium tetrakis(pentafluorophenyl)borate was not used, toobtain 0.96 g of a copolymer. The polymerization activity was 1.05Kg/gZr.

The obtained copolymer had a norbornene content of 11.5 mol %; and anintrinsic viscosity of 2.32 dl/g.

Reference Example 2

The procedures of Example 27 were repeated except that 3.0 mmol ofmethylaluminoxane was employed instead of triisobutylaluminum, andferrocenium tetrakis(pentafluorophenyl)borate was not employed, toobtain 10.4 g of a copolymer. The polymerization activity was 7.6Kg/gZr.

The obtained copolymer had a norbornene content of 8.5 mol %; and anintrinsic viscosity of 2.19 dl/g.

Example 118

The procedures of Example 16 were repeated except that 0.03 mmol ofdimethylanilinium tetrakis(pentafluorophenyl)borate was employed insteadof ferrocenium tetrakis(pentafluorophenyl)borate, to obtain 26.4 g of acopolymer. The polymerization activity was 10 Kg/gZr.

The obtained copolymer had a norbornene content of 7.0 mol %; and anintrinsic viscosity of 3.94 dl/g. The DSC measurement (temperaturedecrease) was made. The results are as shown in FIG. 5.

Comparative Example 18

The procedures of Comparative Example 11 were repeated except that theethylene pressure was changed to 7 Kg/cm², to obtain 35.9 g of acopolymer. The polymerization activity was 0.88 Kg/gZr.

The obtained copolymer had a norbornene content of 6.8 mol %; and anintrinsic viscosity of 3.28 dl/g. The DSC measurement (heat down stage)was made. The results are as shown in FIG. 6.

Example 119

The procedures of Example 46 were repeated except that 0.002 mmol of(3,5-dimethylphenoxy)trichlorozirconium was used instead ofbis(cyclopentadienyl)dihydridezirconium, to obtain 53.7 g of acopolymer. The polymerization activity was 295 Kg/gZr.

The obtained copolymer had a norbornene content of 4.9 mol %; and anintrinsic viscosity of 1.88 dl/g.

[Industrial Applicability]

As described above, according to the process of the present invention, acyclic homopolymer or a cyclic olefin/alpha-olefin copolymer can beeffectively produced without opening the rings of the cyclic olefin andwithout using a great amount of organometalic compounds.

The cyclic olefin copolymers (I) of the present invention are superiorin heat resistance, transparency, strength and hardness, and thus can beeffectively used in an optical, medical and food field or the like.

The cyclic olefin copolymers (II) of the present invention have a goodelongation recovery property, good transparency, suitable elasity andwell-balanced physical properties, and thus can be effectively used asmaterials for films, sheets and other various molded articles in apackaging, medical and agricultural field or the like.

Furthermore, the cyclic olefin copolymer compositions of the presentinvention can be employed in various applications such as a sealantfilm, pallet stretch film, wrapping film for industry use, films foragricultural use, wrapping films for meat, shrink films, coatingmaterials, damping materials, pipes, packages for transfusion liquidsand toys because of their superiority in transparency, an elongationrecovery property, adhesiveness, stabbing strength, tear strength,weatherability, low temperature heat sealability, heat seal strength, ashape memory property, a dielectric property and the like. Inparticular, in the case of molding the cyclic olefin copolymercomposition into films or sheets, the obtained films and sheets willtend not to generate blocking and will have a good elongation recoveryproperty, transparency and adhesiveness. Thus, the sheets and films canbe effectively employed in various fields such as packaging, medical andagricultural fields.

We claim:
 1. A process for producing a cyclic olefin based polymerwherein homopolymerization of a cyclic olefin or copolymerization of acyclic olefin and an alpha-olefin is carried out in the presence of acatalyst comprising as main components the following compounds (A) and(B):(A) a transition metal compound; and (B) a compound capable offorming an ionic complex when reacted with said transition metalcompound,wherein Compound (A) is a transition metal compound representedby the following formula:

    M.sup.1 R.sup.1 R.sup.2 R.sup.3 R.sup.4

wherein M¹ is a transition metal selected from the IVB Group of thePeriodic Table; R¹, R², R³, and R⁴ may be the same as or different fromeach other, and are independently a ligand having a sigma bond, chelateligand or Lewis base.
 2. A process according to of claim 1, whereinCompound (B) is a compound comprising a cation and an anion wherein aplurality of functional groups are connected to an element.
 3. A processaccording to claim 2, wherein Compound (B) is composed of a cationcomprising an element selected from the groups of IIIB, IVB, VB, VIB,VIIB, VIII, IA, IB, IIA, IIB and VIIA of the Periodic Table; and ananion wherein a plurality of functional groups are connected to anelement selected from the groups of VB, VIB, VIIB, VIII, IB, IIB, IIIA,IVA and VA of the Periodic Table.
 4. A process for producing a cyclicolefin based polymer wherein homopolymerization of a cyclic olefin orcopolymerization of a cyclic olefin and an alpha-olefin is carried outin the presence of a catalyst comprising as main components thefollowing compounds (A) and (B):(A) a transition metal compound; (B) acompound capable of forming an ionic complex when reacted with saidtransition metal compound; and (C) an organoaluminum compound, whereinCompound (A) is a transition metal compound represented by the followingformula:

    M.sup.1 R.sup.1 R.sup.2 R.sup.3 R.sup.4

wherein M¹ is a transition metal selected from the IVB Group of thePeriodic Table; R¹, R², R³, and R⁴ may be the same as or different fromeach other, and are independently a ligand having a sigma bond, chelateligand or Lewis base.
 5. A process according to claim 4, whereincompound (B) is a compound comprising a cation and an anion wherein aplurality of functional groups are connected to an element.
 6. A processaccording to claim 5, wherein compound (B) is composed of a cationcomprising an element selected from the group consisting of IIIB, IVB,VB, VIB, VIIB, VIII, IA, IB, IIA, IIB AND VIIA of the Periodic Table;and an anion wherein a plurality of functional groups are connected toan element selected from the group consisting of VB, VIB, VIIB, VIII,IB, IIB, IIIA, IVA and VA of the Periodic Table.
 7. A cyclic olefincopolymer having (1) 80 to 99.9 mol % of the repeating unit [X] ##STR7##wherein R^(a) is hydrogen or a C₁₋₂₀ hydrocarbon group and 0.1 to 20 mol% of the repeating unit [Y]: ##STR8## wherein R^(b) to R^(m), which maybe the same or different from each other, are each independentlyhydrogen, a C₁₋₂₀ hydrocarbon group or a substituent having a halogenatom, oxygen atom or nitrogen atom; R^(j) or R^(k) and R^(l) or R^(m)may form a ring together, and n is 0 or an integer value; (2) anintrinsic viscosity of 0.005 to 20 dl/g; (3) a glass transitiontemperature of less than 20° C.; (4) a tensile modulus ranging from 300to 2,000 kg/cm², determined by measurement at room temperature, and (5)a molecular weight distribution M_(W) /M_(n) of about 1.3 to
 3. 8. Acyclic olefin copolymer according to claim 7, which has a melt peakmeasured by DSC (temperature decrease stage) of less than 90° C.
 9. Acyclic olefin copolymer according to claim 7 or 13, which has acrystallization peak measured by DSC (temperature decrease stage) suchthat the sub peak appears on the high temperature side of the main peak.10. A molded article prepared from a cyclic olefin copolymer of claim 7,or
 8. 11. A molded article according to claim 10, which is formed in theshape of film or sheet.
 12. The molded article of claim 11, wherein saidfilm or sheet has a haze of 9.4 or less.
 13. A molded article accordingto claim 10, which is formed in the shape of wrapping film.
 14. Themolded article of claim 13, wherein said wrapping film has a haze of 9.4or less.
 15. A molded article according to claim 10, which is formedwith a mold.
 16. A cyclic olefin copolymer composition comprising (a)100 parts by weight of a cyclic olefin copolymer of claim 7 or 8; and(b) 0.01 to 10 parts by weight of an anti-blocking agent and/or alubricant.
 17. A cyclic olefin copolymer composition comprising (a) 100parts by weight of a cyclic olefin copolymer of claim 7 or 8; (b) 0.01to 10 parts by weight of an anti-blocking agent and/or a lubricant; and(c) 1 to 100 parts by weight of an alpha-olefin based polymer.
 18. Afilm or sheet prepared from a cyclic olefin copolymer composition ofclaim
 16. 19. A film or sheet prepared from a cyclic olefin copolymercomposition of claim 17.